CN100464840C

CN100464840C - Cobalt-substituted chromium oxide compositions, their preparation, and their use as catalysts and catalyst precursors

Info

Publication number: CN100464840C
Application number: CNB038199238A
Authority: CN
Inventors: V·N·M·劳; D·H·罗森菲尔德; S·苏布拉莫尼; M·A·苏布拉马尼安; A·C·西弗特
Original assignee: EI Du Pont de Nemours and Co
Current assignee: Chemours Co FC LLC
Priority date: 2002-08-22
Filing date: 2003-08-21
Publication date: 2009-03-04
Anticipated expiration: 2023-08-21
Also published as: JP5133500B2; CN1713956A; JP2005536424A; US20050228202A1; WO2004018093A3; EP1539347B1; RU2005107797A; RU2318594C2; EP1539347A2; AU2003265591A1; US7217678B2; WO2004018093A2

Abstract

A crystalline alpha-chromium oxide where from about 0.05 atom % to about 6 atom % of the chromium atoms in the alpha-chromium oxide lattice are replaced by trivalent cobalt (Co<+3>) atoms is disclosed. Also disclosed is a chromium-containing catalyst composition comprising as a chromium-containing component the crystalline cobalt-substituted alpha-chromium oxide; and a method for preparing a composition comprising the crystalline cobalt-substituted alpha-chromium oxide. The method involves (a) co-precipitating a solid by adding ammonium hydroxide to an aqueous solution of a soluble cobalt salt and a soluble trivalent chromium salt that contains at least three moles of nitrate per mole of chromium in the solution and has a cobalt concentration of from about 0.05 mole % to about 6 mole % of the total concentration of cobalt and chromium in the solution; and after at least three moles of ammonium per mole of chromium in the solution has been added to the solution, (b) collecting the co-precipitated solid formed in (a); (c) drying the collected solid; and (d) calcining the dried solid.Also disclosed is a chromium-containing catalyst composition comprising a chromium-containing component prepared by treating the crystalline cobalt-substituted alpha-chromium oxide with a fluorinating agent; and a process for changing the fluorine distribution (i.e., content and/or arrangement) in a hydrocarbon or halogenated hydrocarbon in the presence of a catalyst. The process involves using as the catalyst a composition comprising the crystalline cobalt-substituted alpha-chromium oxide and/or the treated cobalt-substituted alpha-chromium oxide.

Description

The chromium oxide compositions that cobalt replaces, their preparation and they are as the purposes of catalyst and catalyst precarsor

Invention field

The present invention relates to contain the application of the catalytic treatment (catalytic processing) that the composition of chromium and their preparation and they are used for hydrocarbon and/or halogenated hydrocarbons.

Background technology

As everyone knows, α-Cr ₂O ₃And α-Fe ₂O ₃All has α-Al ₂O ₃The structure of (corundum), i.e. M ^{+ 3}Ion occupies octahedral position in the closelypacked oxide lattice of six sides., CoO has the lattice similar to NaCl, and Co ₃O ₄Has the normal spine structure.In the agreement (treatises) of standard, these basic structure has been described; For example, see the 538th of StructuralInorganic Chemistry, 543-545 and 550 pages, A.F.Wells, the 5th edition, Clarendon Press, Oxford, UK (1986).At Wilhelmi, ActaChemica Scandinavica, the 22nd volume has been described gamma oxidation chromium (CrO in the 2565-2573 page or leaf _2.44).

Prepared the mixed-metal oxides that the cation position of many lattices is occupied by different metal.For example, known (Cr _xFe _1-x) ₂O ₃The solid solution of type, wherein 0＜x＜has 1. prepared these materials by the pottery or the sol-gel process of standard, as people such as Music, at J.Materials Science, the 31st volume is in the 4067-4076 page or leaf (1996) and people such as Bhattacharya, at J.Materaials Science, the 32nd volume is described in 577-560 (1997) page or leaf.

Mixed C r-Co oxide with spinel structure is knownly (for example, to see people such as Bracconi, Ann.Chim.Fr., the 4th volume, 331-338 page or leaf (1979) and Hanck and Laitinen, J.Inorg.Nucl.Chem., the 33rd volume, 63-73 page or leaf (1971)).

CrCoO ₃Interconnector material (seeing Chem.Abs.118:9397) in the battery component acts as a fuel.People such as Castiglioni, J.Solid State Chemistry, the 152nd volume, 526-532 (2000); People such as Nowotny, J.Am.Ceram.Soc., the 65th volume, people such as 192-196 page or leaf (1982) and Zhang, Journal of Power Sources, the 83rd volume also discloses the various mixed-metal oxides that contain cobalt and chromium in the 121-127 page or leaf (1999).

Use some metal oxide as catalyst and/or catalyst precarsor in the fluorinated hydrocarbons manufacturing.Chromium oxide (III) is useful especially, because have been found that, it at high temperature can be fluoridized by HF, thereby produce the mixture of charomic fluoride and fluorine chromium oxide, and this mixture is having under the situation of HF, be the effective catalyst that is used for the C-C1 key is converted into the C-F key. this is converted into the C-F key with the C-C1 key and is commonly referred to halogen exchange under the effect of HF, be the committed step in many fluorine hydrogen compound manufacture processes.

The chromium oxide compositions or the said composition that can prepare in several ways as catalyst precarsor can present various ways.Can pass through the green dehydration of Guignet ' s or chromium (III) salt be precipitated to prepare the chromium oxide (seeing U.S. Pat 3,258,500) that is applicable to gas phase fluorination by reduction chromium trioxide (VI) with alkali.The chromium oxide of another kind of useful form is the low six side's hydroxide chromium oxide (chromium oxide hydroxide) of alkali metal ion content measured, as U.S. Pat 3,978, disclosed in 145. as U.S. Pat 3, disclosed in 992,325, with compound such as MF ₄(M=Ti, Th, Ce), MF ₃(M=Al, Fe, Y) and MF ₂(M=Ca, Mg, Sr, Ba, Zn) joins in six side's hydroxide chromium oxide increases catalyst life.The chromium oxide that is especially effectively a kind of form of fluorination catalyst precursor is the chromium oxide by ammonium dichromate pyrolysis preparation, and is as U.S. Pat 5,036, disclosed in 036.

Disclose in chromium-based fluorination catalyst load and/or not load and (for example added other compound, other slaine). Australian patent document AU-A-80340/94 discloses based on chromium oxide (or oxide of chromium) and the bulk of at least a other catalytically-active metals (for example Mg, V, Mn, Fe, Co, Ni or Zn) or the catalyst of load, wherein the major part of oxide be crystalline state (and, when this catalyst is bulk catalyst, after with the HF activation, its specific surface is at least 8m ²/ g).Disclosed crystalline phase comprises Cr ₂O ₃, CrO ₂, NiCrO ₃, NiCrO ₄, NiCr ₂O ₄, MgCrO ₄, ZnCr ₂O ₄With these hopcalites.Australian patent document AU-A-29972/92 discloses a kind of bulk catalyst based on chromium oxide and nickel oxide, wherein nickel/chromium atom is (more optional than the fluorination catalyst that discloses based on chromium oxide for 0.05-5. U.S. Patent Application Publication US2001/0011061 A1, contain Mg, Zn, Co and Ni), wherein chromium oxide is partially crystallizable at least.The fluorination catalyst (for example, being immersed on the carrier) that contains the combination of cobalt and chromium is in U.S. Pat 5,185, disclosed catalyst in 482.U.S. Pat 5,559,069 disclose the even dispersion multiphase catalyst composition of the decentralized photo that is characterised in that some divalent metal fluoride (some fluoride of Mn, Co, Zn, Mg and/or Cd) and some trivalent metal fluoride (fluoride of Al, Ga, V and/or Cr).

Also need to be used for halogen exchange catalyst: the fluoridizing and chlorofluorination of saturated and unsaturated hydrocarbons, chlorohydrocarbon, fluorine chlorohydrocarbon and CFC such as following process; Fluoridizing of unsaturated fluorohydrocarbon; The isomerization of fluorinated organic compounds and disproportionation; The chlorination defluorinateization (chlorodefluorination) of the dehydrofluorination of fluorohydrocarbon and fluorocarbons.

Summary of the invention

The chromium atom that the invention provides the about 6 atom % of about 0.05-in a kind of alpha-oxidation chromium lattice is by trivalent cobalt (Co ³⁺) crystalline alpha-chromium oxide of replacing of atom and a kind ofly comprise described crystallization cobalt and replace alpha-oxidation chromium as the chromium-containing catalyst composition that contains the chromium component.

The present invention also provides a kind of preparation to contain the method for compositions that described crystallization cobalt replaces alpha-oxidation chromium. and this method comprises that (a) makes the solid co-precipitation by add ammonium hydroxide (ammoniacal liquor) in the solution of solvable cobalt salt and solvable chromic salt, this solution whenever has 1 mole of chromium (that is Cr, in solution ^{+ 3}) just contain at least 3 molar nitric acid root (that is NO, ₃ ^-), the concentration of cobalt is the about 6 moles of % of about 0.05-of chromium and cobalt total concentration in the solution; At every mole of chromium (that is Cr, ^{+ 3}) at least 3 molar ammoniums (that is NH, ₄ ⁺) join in the solution after; (b) be collected in the solid of the co-precipitation that forms in (a); (c) the dry solid of collecting; The solid of (d) calcination drying.

It is a kind of by handling the chromium-containing catalyst composition that contains the chromium component that described crystallization cobalt replaces the preparation of alpha-oxidation chromium with fluorization agent (for example, hydrogen fluoride) that the present invention also provides.

The present invention also provides a kind of and changes the distribute method of (that is, content and/or arrangement) of fluorine having under the situation of catalyst in hydrocarbon or halogenated hydrocarbons.The use that is characterized as of this method contains at least a composition that contains the chromium component as catalyst, and the described chromium component that contains is selected from the cobalt replacement alpha-oxidation chromium that described crystallization cobalt replaces alpha-oxidation chromium and described processing.

The accompanying drawing summary

Nominally Fig. 1 is the energy that contains the cobalt replacement alpha-oxidation chromium sample of 2 atom % cobalts to be disperseed to compose (energy dispersive spectroscopy, EDS).

Fig. 2 is the EDS spectrum that does not have the alpha-oxidation chromium sample of cobalt replacement.

Fig. 3 is the EDS spectrum of cobalt picotite sample.

Fig. 4 be with around (a) and (b), (c), (d) radial distribution function relevant (that is) curve, at a certain probability of distance central atom, (a) the cobalt central atom among the CoO, (b) Co apart from an atom of r place discovery with local atomic structure (e) ₃O ₄In cobalt central atom, (c) Cr ₂O ₃In chromium central atom, (d) nominally replace cobalt in the alpha-oxidation chromium sample nominally contain cobalt that the cobalt of 2 atom % cobalts replaces the cobalt in the alpha-oxidation chromium sample and (e) contain 10 atom % cobalts.

Detailed Description Of The Invention

New compositions of the present invention comprises and keeps the cobalt that contains in the about 6 atom % cobalts of about 0.05-of the total amount of cobalt and chromium in the alpha-oxidation chromium of corundum structure to replace alpha-oxidation chromium. the present invention includes and contain described crystallization cobalt replacement α-Cr₂O ₃Catalyst composition. The crystallization cobalt replaces the general formula of alpha-oxidation chromium Be α-Co_xCr _2-xO ₃, wherein x is 0.001-0.12.

Can prepare composition of the present invention by the said method that uses co-precipitation. Typically In the coprecipitation, the aqueous solution of preparation cobalt (II) salt or cobalt (III) salt and chromium (III) salt. The relative concentration of cobalt salt and chromium (III) salt by cobalt required in the final catalyst mutually in the aqueous solution Volume (bulk) % by mole decision for chromium. The concentration typical case of chromium in the aqueous solution (III) Be 0.3-3 volume mole (mol/L), 0.75-1.5 volume mole is preferred concentration. Chromium (III) salt that is applicable to the preparation aqueous solution is nitrate, sulfate, acetate, formic acid The various hydrated forms of salt, oxalate, phosphate, bromide and chloride and these salt. Other chromium (III) salt for the preparation of the aqueous solution comprises formula [CrL_6-zA _z] ^+3-ZSix coordinate complex, wherein each L is neutral (that is, uncharged) ligand, is selected from H₂O、NH ₃、C ₁-C ₄The primary, the second month in a season or uncle's organic amine, C₁-C ₄Alkyl nitrile or pyridine, wherein each A is anion ligand, Be selected from fluorine ion, chlorion, bromide ion, iodide ion, hydroxyl, nitrite anions and nitrate anion, Wherein the value of Z is 0-3 (containing end value). Comprise the neutral bidentate ligand that is equivalent to two L Such as ethylenediamine, because they can occupy two coordination positions. comprise that also can occupy two joins Anion bidentate ligand such as the C of position, position₁-C ₄Carboxylate radical. Comprise that also being equivalent to two A joins The position body also can occupy dianion (dianionic) ligand that surpasses a coordination position Such as sulfate radical.

The salt of alkali metal containing such as potassium chromium sulfate are not preferred, because alkali-metal existence meeting overslaugh Catalyst activity (seeing U.S. Pat 4,843,181). Chromium (VI) precursor such as CrO₃Although Not preferred, but can use, but need to before precipitation, be reduced into compound such as ethanol Cr (III).

Chromic nitrate (III) or its hydrated form are such as [Cr (NO₃) ₃(H ₂O) ₉] be most preferred for Chromium (III) salt for preparing the described aqueous solution.

Cobalt (II) salt that is applicable to this aqueous solution of preparation is the various hydrated forms of nitrate, sulfate, formates, oxalate, bromide, chloride and these salt.The salt of alkali metal containing is not preferred as two cobaltous potassium sulfates, because alkali-metal existence meeting overslaugh catalyst activity. nitric hydrate cobalt (II) (for example, [Co (NO ₃) ₂(H ₂O) ₆]) be most preferred cobalt (II) salt.

Cobalt (III) salt that is used to prepare this aqueous solution comprises formula [CoL _6-zA _z] ^{+ 3-Z}Six coordinate complex, wherein each L is neutral (that is, uncharged) ligand, is selected from H ₂O, NH ₃, C ₁-C ₄The primary, the second month in a season or uncle's organic amine, C ₁-C ₄Alkyl nitrile or pyridine, wherein each A is an anion ligand, be selected from fluorine ion, chlorion, bromide ion, iodide ion, hydroxyl, nitrite anions and nitrate anion, wherein the value of Z is 0-3 (containing end value). comprise the neutral bidentate ligand such as the ethylenediamine that are equivalent to two L, because they can occupy two coordination positions. also comprise the anion bidentate ligand such as the C that can occupy two coordination positions ₁-C ₄Carboxylate radical.Also comprise and be equivalent to two A ligands and can occupy dianion ligand such as the sulfate radical that surpasses a coordination position.Preferred cobalt (III) parent material is six ammonia salt (for example, [Co (NH ₃) ₆] ^{+ 3}, wherein counter ion is chlorion or nitrate anion. and chlorination six ammonia cobalt (III) (for example, [Co (NH ₃) ₆] Cl ₃]) be most preferred cobalt (III) salt.

Then, under vacuum or high temperature, evaporate the aqueous solution of cobalt salt and chromium (III) salt to produce solid, calcination then.

Yet, preferably, with alkali such as ammonium hydroxide (ammoniacal liquor) handle cobalt salt and chromium (III) salt the aqueous solution so that cobalt and chromium with the form precipitation of hydroxide. can use alkali such as NaOH or the potassium hydroxide or the carbonate of alkali metal containing, but not be preferred. adding ammonium hydroxide carries out in 1-12 hour time typically gradually in the aqueous solution of cobalt and chromium (III) salt.In the process that adds alkali, monitor the pH value of solution.Final pH value is typically 6.0-11.0, and preferably about 7.5-is about 9.0, most preferably from about 8.0-8.7.Typically, about 60 ℃ at about 15-, carry out the precipitation of cobalt hydroxide/chromium hydroxide mixture under about 40 ℃ of preferably about 20-. after adding ammonium hydroxide, typically stir this mixture up to 24 hours.

What paid close attention to is to have the preparation of (that is, surpassing 3 molar nitric acids ammonium/mole chromium) of excessive ammonium nitrate in the aqueous solution.For example, the ammonium nitrate that in reaction, has existed from ammonium hydroxide and chromic nitrate, can be before the composition co-precipitation, among or afterwards every mole of about 7.0 moles extra ammonium nitrate of the about 0.1-of chromium is joined in the solution. unexpectedly, we find, can be used to reduce α-Co adding excessive ammonium nitrate before the dehydration in the mixture of the cobalt hydroxide of precipitation and chromium hydroxide _xCr _2-xO ₃The particle diameter of phase, this make again the surface area of this phase and catalyst activity increase (see preparation embodiment 15,17 and 18 and embodiment 20,21,30 and 31).

After joining ammonium nitrate in the mixture, preferably under the about 60 ℃ temperature of about 20-stir about 0.5-10 hour (preferably about 1-5 hour).Then, this mixture of drying as follows and calcination.

Other reagent that is used for this purpose comprises that aqueous hydrogen peroxide (1-30% solution), ozone, peroxy acid are as Peracetic acid and ammonium persulfate. can use such as the reagent the halogen, but not be preferred.The reagent of alkali metal containing such as potassium peroxydisulfate or sodium perborate also can use but not be preferred.

After the mixture precipitation of cobalt hydroxide and chromium hydroxide is finished, if desired, add ammonium nitrate or other reagent, by this mixture of evaporation drying.

Randomly, cobalt hydroxide and chromium hydroxide mixture that can collecting precipitation if desired, spend deionised water before drying. and this can influence activity of such catalysts (seeing embodiment 32 and 33).

After dry hydrogen cobalt oxide and chromium hydroxide mixture, by solid is heated to about 350 ℃ from about 250 ℃ nitrate is decomposed then. then, about 1000 ℃ at about 375-, the about 600 ℃ of solids that following calcination obtains of preferably about 400-.When using catalyst to change the distribution of fluorine in hydrocarbon and halogenated hydrocarbons, calcining heat can influence activity of such catalysts, thereby and influence product distribution (seeing embodiment 34 and 35).Lower calcining heat can cause existing some remaining nitrate impurity.

Preferably in the presence of oxygen, most preferably in the presence of air, calcine.

Metal oxide composition of the present invention can characterize by the analytical technology of generally acknowledging, comprises that X-x ray absorption spectrum x (XAS), X-ray powder diffraction (XRD), transmission electron microscope art (TEM) and energy disperse spectroscopy (EDS).It is available analysis tool that EDS combines with scanning or analysis TEM.

After the calcining, the crystal that the cobalt that obtains replaces by TEM with the naked eye can not with α-Cr ₂O ₃Distinguish.And, X-ray and electron diffraction investigation and α-Cr ₂O ₃Structure is in full accord, and this structure has with the proportional lattice of the amount that replaces the cobalt (III) of Cr (III) in the structure shrinks.Therefore, infer that said composition has general formula α-Co _xCr _2-xO ₃, wherein x is 0.001-0.12.

Clearly represent the existence of cobalt in the various cobalts of the present invention/chromium composition by the elementary analysis of using EDS.Nominally Fig. 1 explanation contains the cobalt of 2 atom % cobalts and replaces α-Cr ₂O ₃The EDS of sample.In order to contrast α-Cr that Fig. 2 explanation does not have cobalt to replace ₂O ₃EDS, Fig. 3 illustrates commercially available CoCr ₂O ₄, among the EDS. of cobalt picotite each figure in this 3 width of cloth figure, the energy level E with kilo electron volt (keV) is drawn in the thousand X-transmitted intensity I that count.Peak among each figure is relevant with the existence of some element.In Fig. 1, in EDS, clearly show the existence of cobalt, and in Fig. 2, do not have the cobalt peak.During the content of cobalt higher (for example, the cobalt body phase composition (bulk composition) that composition has is greater than the about 6 atom % cobalts in total metal contents in soil), name consists of (Cr _0.5Co _0.5) ₃O ₄And crystal size is that second spinel-like of 10nm is picked out by TEM and EDS mutually easily.The K of Cr among Fig. 3 (atomic weight 52) and Co (atomic weight 59) _αThe relative altitude of the 2:1 of peak value represents that the EDS data are effective on quantitative basis.

Nominally obtained the XAS and the XRD data of the composition of 100%Cr (not adding cobalt), Cr98%/Co2%, Cr95%/Co5% and Cr90%/Co10%.XAS and XRD analysis clearly illustrate that cobalt substitutes onto α-Cr ₂O ₃In.The XRD of Cr98%/Co2% the results are shown in the table 1.Diffraction maximum with spacing d of 3.1368,1.9211,1.3581,1.2464 and 1.1088 is owing to join in the sample, be used to calibrate in the silicon of diffractometer due to the mark.Can be with all other diffraction maximum index be α-Cr that unit cell volume reduces slightly ₂O ₃Structure.

Table 1

Nominally the Co of 98 atom %Cr/2 atom %Co replaces α-Cr ₂O ₃The XRD result of composition

D (dust) Highly FWHM ^a

3.6263 134 0.627

3.1368 2539 0.135

2.6635 288 0.607

2.4656 668 0.448

2.2550 53 0.312

2.1661 292 0.450

2.0430 16 0.469

1.9211 1842 0.136

1.8105 128 0.634

1.6654 707 0.510

1.6382 1076 0.223

1.5772 37 0.202

1.4644 98 0.533

1.4260 289 0.579

1.3581 274 0.195

1.2907 92 0.762

1.2464 460 0.159

1.2352 55 0.566

1.2055 44 0.516

1.1486 40 0.283

1.1238 38 0.362

1.1088 689 0.162

1.1059 272 0.215

A.FWHM is the overall with at half place of maximum.

If Co replaces α-Cr ₂O ₃Cr mutually estimates that then it is octahedral coordination (N Co-0=6), and is+3 oxidation state. the XAS result on the Cr-K limit of sample shows that all Cr are with Cr ³⁺Form exist, and be octahedral coordination.If cobalt be present in electron microscope observation to spinel-like mutually in, then some in these atoms will have tetrahedral coordination, and exist with the form of+2 oxidation state.

Fig. 4 has illustrated the radial distribution function (RDF) of 5 kinds of materials.Radial distribution function is illustrated in apart from a certain probability of finding an atom apart from the r place of central atom. by depending on these probability of factor weighting of atomic type.Therefore, RDF is the performance around the local atomic structure of central atom.Fourier transformation by extension X-radiation absorption fine structure (EXAFS) data obtains RDF, and can represent the curve of separating distance dust by dimensionless numerical value F.In brief, the peak among the RDF figure can be considered as in expression around the distance of the coordination ball of central atom. when because the phase shift that is scattered of excitation electron and when revising, estimating has small difference between the spacing of reality " r " to that indicated in the drawings.In Fig. 4, in 5 kinds of materials each, with respect to spacing r (representing that with dust phase shift is not revised) is drawn F.Comprise among Fig. 4 that curve A represents the partial structurtes of cobalt in the Co0; Curve B is represented around Co ₃O ₄The partial structurtes of middle cobalt; Curve C is represented around α-Cr ₂O ₃The partial structurtes of middle chromium.Comprise also among Fig. 4 that curve D represents to replace around the cobalt that name consists of 98% chromium and 2% cobalt the partial structurtes of cobalt in the alpha-oxidation chromium, represent to center on the partial structurtes that the nominal cobalt that consists of 90% chromium and 10% cobalt replaces cobalt in the alpha-oxidation chromium with curve E. in this sample, do not detect the spinelle phase by electron microscopy, therefore think all Co all with α-Cr ₂O ₃Mutually relevant, perhaps as separation of oxygenated cobalt coating, perhaps as α-Cr ₂O ₃The substitute of Cr in the lattice.The curve that the cobalt that expression consists of 98% chromium and 2% cobalt around name among Fig. 4 replaces the partial structurtes of cobalt in the alpha-oxidation chromium shows, the common cobalt oxide of the local atomic structure of Co and expectation dissmilarity mutually in this sample, and with α-Cr ₂O ₃The local atomic structure of mutually middle Cr is closely similar.

Table 2 has shown by the XAS of CoK limit absorption spectra analyzes average first neighbour's ligancy (N Co-0) of obtaining and average Co oxidation state and the class alpha-oxidation chromium unit cell volume mutually by the XRD acquisition.

Table 2

The sign of the alpha-oxidation chromium (III) that metal replaces

Form the average Co unit cell volume of Cr/Co

Atom % N (Co-0) oxidation state (nm ³)

Cr100％ 100/0 0.284839

Cr98％Co2％ 98/2 6.01 2.940 0.284614

Cr95％Co5％ 95/5 5.67 2.840 0.284268

Cr90％Co10％ 90/10 5.46 2.634 0.284177

Consider that ionic radius is appreciated that unit cell volume reduces when introducing Co.If Co ^{+ 3}Replace and enter α-Cr ₂O ₃Middle Cr ^{+ 3}Octahedral environment, they will take low spin structure, as Cotton at Chemical Applications of Group Theory, the 3rd edition (New York, Wiley, 1990) discuss in the 8th chapter. use as Shannon and Prewitt at ActaCrystallographica, B25 rolls up, the high-spin Cr that provides in the 925-945 page or leaf (1969) ^{+ 3}(62pm), low spin Co ^{+ 3}(53pm) and O ^-2Ionic radius (137pm), unit cell volume reduce and replace α-Cr ₂O ₃High-spin Cr in the lattice ^{+ 3}Low spin Co ^{+ 3}Amount relevant.These relation generalizations are in table 3, and table 3 has illustrated the composition that replaces for 4 kinds of Co, enter α-Cr based on the actual replacement of ligancy, oxidation state and unit cell volume ₂O ₃Cobalt amount mutually.Data in the table 3 are very consistent, and its expression cobalt is at α-Cr ₂O ₃Solubility limit mutually is the further indication that the curve among about 6 atom %. Fig. 4 provides the cobalt total concentration to surpass the cobalt solubility limit of 6 atom %, the figure shows the partial structurtes that replace cobalt in the alpha-oxidation chromium around the nominal cobalt that consists of 90% chromium and 10% cobalt.This curve shows that some cobalts are with Co ₃O ₄Form exist.

Table 3

The replacement of various compositions enters α-Cr ₂O ₃The replacement of the amount cobalt of cobalt enters α-Cr in the lattice ₂O ₃Atom % in the lattice

Composition based on N (Co-0) according to the Co oxidation state based on unit cell volume

Cr98％/Co2％ 2.00(0.15) 1.82(0.03) 1.72(0.4)

Cr95％/Co5％ 3.75(0.38) 3.80(0.08) 4.37(0.4)

Cr90％/Co10％ 5.94(o.75) 4.51(0.15) 5.06(0.4)

In chromium oxide compositions of the present invention, can exist other mutually as chromium cobalt spinel phase.Detect by EDS and TEM and to exist total stoichiometric proportion for (Co _0.5Cr _0.5) ₃O ₄These phases.These are mutually usually with respect to class α-Cr ₂O ₃Mutually less, and have smaller particle size usually.

The surface area of chromium oxide compositions of the present invention is typically about 1-100m ²/ g.α-the Co that exists in the composition by the inventive method preparation _xCr _2-xO ₃Be the about 400nm of about 20-by particle diameter typically mutually, the crystal of the about 250nm of typically about 40-constitutes. the present invention includes the micro crystal material of particle diameter less than 20nm.

The extrudate that the chromium oxide compositions of the present invention of calcination can form different shape such as bead, particle and use for the packing reactor. it also can use with form of powder.

The activity of such catalysts that obtains behind the mixed-metal oxides is fluoridized in the cobalt content influence of chromium oxide compositions of the present invention.For example, with CCl ₂=CClCF ₃Chlorofluorination is CF ₃CClFCF ₃In, for the chrome catalysts that does not contain cobalt,, be used to form CF owing to have the composition of 2-5 atom % cobalt in the catalyst ₃CClFCF ₃The activity of the metal oxide catalyst of fluoridizing that contains cobalt and chromium improved (seeing Table 4).And, consistent with instruction of the present invention, can improve the activity that contains to the composition of fixed-ratio cobalt and chromium by initial soln before dehydration and calcining with reagent such as ammonium nitrate treatment of nitric acid cobalt (II) and chromic nitrate (III).

Table 4

Be used for CCl ₂=CClCF ₃Chlorofluorination is

CF ₃CClFCF ₃ ^aThe activity of fluorinated cobalt/chromium

Cr/Co is than in 400 ℃ of following products of calcining heat

CF ₃CClFCF ₃％

100/0 400℃ 24.1

99/1 400℃ 47.4

98/2 400℃ 46.6

98/2 550℃ 36.7

9,7/3 400 ℃, washed 31.7

9,5/5 400 ℃, excessive NH ₄NO ₃27.6 ^B.

A. prepare catalyst by the coprecipitation of using ammonia.HF, 1213xa and Cl ₂Molar feed ratio be 30:1:2.

B. temperature of reactor is 350 ℃.

The cobalt picotite is not considered to be used to fluoridize or the effective catalyst (seeing Comparative Examples 26) of chlorofluorination reaction.

Composition of the present invention can also comprise one or more form of metal compound, change the crystallization cobalt and replace alpha-oxidation chromium or contain cobalt and the selectivity of the metal fluoride oxide catalyst of chromium or active additive.Suitable additive is selected from fluoride, oxide or the oxyfluoride of Mg, Ca, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Ce and Zn.

In the total metal content of composition, additive level is the about 15 atom % of about 0.05-in the present composition.Can as dipping additive be introduced in the composition of the present invention by standard method.

Typically, before as the catalyst that changes fluorine distribution in hydrocarbon and/or the halogenated hydrocarbon compound, composition with fluorization agent preliminary treatment calcination. typically, this fluorization agent is HF, although can use other material such as sulfur tetrafluoride, carbonyl fluoride and fluorinated hydrocarbons compound such as Arcton 11, dicholorodifluoromethane, dichlorodifluoromethane, fluoroform or 1,1, the 2-trichorotrifluoroethane. for example, can be by catalyst be put into suitable containers, after this, make HF pass through drying, the catalyst of calcination is to make this catalyst member saturated and realize that this preliminary treatment, described suitable containers can be the reactors that is used to carry out the inventive method with HF.This is by making HF through catalyst a period of time under the temperature that for example about 200-is about 450 ℃, however about 10 hours of for example about 0.1-and carrying out easily., this preliminary treatment is dispensable.

As mentioned above, catalyst provided by the invention can be used for changing the distribution of fluorine at hydrocarbon and/or halogenated hydrocarbons.Can change the distribution of fluorine in hydrocarbon or halogenated hydrocarbons by fluorine content in raising hydrocarbon or the halogenated hydrocarbons.Also can distribute by reducing the fluorine content in the halogenated hydrocarbons and/or resetting the fluorine that the position of fluorine atom on the halogenated hydrocarbons carbon atom change in the halogenated hydrocarbons.What paid close attention to is to change the method that fluorine distributes in the halogenated hydrocarbons that contains 1-12 carbon atom, particularly changes the method that fluorine distributes in the halogenated hydrocarbons that contains 1-6 carbon atom.What also paid close attention to is the method that improves fluorine content in the hydrocarbon contain 1-12 carbon atom, particularly improves the method for fluorine content in the hydrocarbon that contains 1-6 carbon atom. the method that the change fluorine distributes in halogenated hydrocarbons comprise fluoridize, chlorofluorination, isomerization, disproportionation, dehydrofluorination and chlorination defluorinateization.The inventive method is characterised in that uses following composition as catalyst, and described composition comprises that at least a crystallization cobalt as mentioned above of being selected from replaces and contains the chromium component in alpha-oxidation chromium and the described cobalt replacement alpha-oxidation chromium of having handled with fluorization agent. be applicable to fluoridize, the typical saturated halogenated hydrocarbon of chlorofluorination, isomerization, disproportionation, dehydrofluorination and chlorination defluorinate process is to have formula C _nH _aBr _bCl _cF _dHalogenated hydrocarbons, wherein n is the 1-6 integer, a is the 0-12 integer, b is the 0-4 integer, c is the 0-13 integer, d is the 0-13 integer, b, c and d's and be at least 1, a, b, c and d sum equal 2n+2, condition is that n is at least 2 for isomerization, disproportionation and dehydrofluorination; For the dehydrofluorination process, a is at least 1; For chlorination defluorinate process, b is 0; For fluorination process, b+c is at least 1; For the dehydrofluorination process, b+c is 0; For fluoridize, chlorination defluorinateization, isomerization, disproportionation and dehydrofluorination process, a+b+c is at least 1; For isomerization, disproportionation, dehydrofluorination and chlorination defluorinate process, d is at least 1.Be applicable to fluoridize, the typical unsaturated halogenated hydrocarbons of chlorofluorination, isomerization, disproportionation and chlorination defluorinate process is to have formula C _pH _eB _rFCl _gF _hHalogenated hydrocarbons, wherein p is the 2-6 integer, e is the 0-10 integer, f is the 0-2 integer, g is the 0-12 integer, h is the 0-11 integer, f, g and h's and be at least 1, and e, f, g and h's and equal 2p, condition is for chlorination defluorinate process, f is 0; For isomerization and dismutation, e+f+g is at least 1; For isomerization, disproportionation and chlorination defluorinate process, h is at least 1. and is applicable to that the typical saturated hydrocarbons of chlorofluorination is to have formula C _qH _rHydro carbons, wherein q is the 1-6 integer, r is 2q+2.Be applicable to that the typical unsaturated hydro carbons of fluoridizing with chlorofluorination is to have formula C _iH _jHydro carbons, wherein i is the 2-6 integer, j is 2i.

Fluoridize

The present invention includes by having under the situation of carbon monoxide-olefin polymeric, described compound and hydrogen fluoride are reacted in gas phase and improve the method for fluorine content in halogenated hydrocarbons or the unsaturated hydrocarbon compound, described carbon monoxide-olefin polymeric comprises that being selected from alpha-oxidation chromium that above-mentioned crystallization cobalt replaces and the described cobalt of having handled with fluorization agent replaces at least a chromium component that contains in the alpha-oxidation chromium.This carbon monoxide-olefin polymeric can randomly contain extra component such as additive to change this activity of such catalysts and selectivity.

The halogenated hydrocarbon compound that is suitable as fluorination process parent material of the present invention can be saturated or unsaturated.The saturated halogenated hydrocarbon compound that is applicable to fluorination process of the present invention comprises that general formula is C _nH _aBr _bCl _cF _dHalogenated hydrocarbon compound, wherein n is the 1-6 integer, a is the 0-12 integer, b is the 0-4 integer, c is the 0-13 integer, d is the 0-13 integer, a, b, c and d's and equal 2n+2, condition is that b+c is at least 1.The unsaturated halogenated hydrocarbon compound that is applicable to fluorination process of the present invention comprises general formula C _pH _eBr _fCl _gF _hCompound, wherein p is the 2-6 integer, e is the 0-10 integer, f is the 0-2 integer, g is the 0-12 integer, h is the 0-11 integer, f, g and h and be at least l, e, f, g and h's and equal 2p.Be applicable to that the unsaturated hydro carbons of fluoridizing is to have formula C _iH _jHydro carbons, wherein i is integer 2-6, j is 2i.Can be by having under the situation of carbon monoxide-olefin polymeric, described compound and HF are reacted in gas phase and improve formula C _nH _aBr _bCl _cF _dSaturated compounds, formula C _pH _eBr _fCl _gF _hUnsaturated compound and/or formula C _iH _jUnsaturated compound in fluorine content, described carbon monoxide-olefin polymeric comprises that being selected from alpha-oxidation chromium that above-mentioned crystallization cobalt replaces and the described cobalt of having handled with fluorization agent replaces at least a chromium component that contains in the alpha-oxidation chromium.In this article, this process is called gas phase fluorination.

Typically, under about 150-500 ℃, carry out gas phase fluorination.For saturated compounds,, more preferably from about fluoridize under about 350 ℃ of the 200-preferably at about 175-400 ℃.For unsaturated compound,, more preferably from about fluoridize under about 300 ℃ of the 175-preferably at about 150-350 ℃.

Typically, under atmospheric pressure and super-atmospheric pressure, carry out gas phase fluorination.For reason easily in the downstream separation process (for example, distillation), can use up to about 30 atmospheric pressure.

Typically, in tubular reactor, carry out gas phase fluorination.Reactor and feed pipe, discharge nozzle and the relevant device relevant with it should be by the material manufacturings of anti-hydrogen fluoride and hydrogen chloride. well-known in the fluorination technology, typical building material comprises stainless steel, particularly Chou Shi build stainless steel, well-known Langaloy as

Corronil,

Nickel-base alloy and Nichrome and the steel that coats copper.

Typically, be about 120 seconds of about 1-time of contact in the reactor, about 60 seconds of preferably about 5-.

Should be at least the amount of stoichiometric proportion with the amount of the HF of unsaturated hydrocarbons or halogenated hydrocarbon compound reaction. the amount of this stoichiometric proportion is based on except being used to make 1 mole of saturated HF of carbon-to-carbon double bond (if existence), treat the Br and/or the substituent number meter of Cl that are replaced by F. typically, HF and described formula C _nH _aBr _bCl _cF _d, C _pH _eBr _fCl _gF _hAnd C _iH _jThe mol ratio of compound be about 0.5:1-100:1, the preferred about 50:1 of about 2:1-, more preferably from about the about 20:1. of 3:1-generally speaking, for given carbon monoxide-olefin polymeric, temperature is high more, time of contact is long more, the conversion ratio that is converted into fluorinated product is just high more. and above-mentioned variable can balance each other, thereby makes the formation maximum of the product of higher fluorine replacement.

Having under the situation of catalyst of the present invention, can with the formula C of HF reaction _nH _aBr _bCl _cF _dThe example of saturated compounds comprise CH ₂Cl ₂, CH ₂Br ₂, CHCl ₃, CCl ₄, C ₂Cl ₆, C ₂BrCl ₅, C ₂Cl ₅F, C ₂Cl ₄F ₂, C ₂Cl ₃F ₃, C ₂Cl ₂F ₄, C ₂ClF ₅, C ₂HCl ₅, C ₂HCl ₄F, C ₂HCl ₃F ₂, C ₂HCl ₂F ₃, C ₂HClF ₄, C ₂HBrF ₄, C ₂H ₂Cl ₄, C ₂H ₂Cl ₃F, C ₂H ₂Cl ₂F ₂, C ₂H ₂ClF ₃, C ₂H ₃Cl ₃, C ₂H ₃Cl ₂F, C ₂H ₃ClF ₂, C ₂H ₄Cl ₂, C ₂H ₄ClF, C ₃Cl ₆F ₂, C ₃Cl ₅F ₃, C ₃Cl ₄F ₄, C ₃Cl ₃F ₅, C ₃HCl ₇, C ₃HCl ₆F, C ₃HCl ₅F ₂, C ₃HCl ₄F ₃, C ₃HCl ₃F ₄, C ₃HCl ₂F ₅, C ₃H ₂Cl ₆, C ₃H ₂BrCl ₅, C ₃H ₂Cl ₅F, C ₃H ₂Cl ₄F ₂, C ₃H ₂Cl ₃F ₃, C ₃H ₂Cl ₂F ₄, C ₃H ₂ClF ₅, C ₃H ₃Cl ₅, C ₃H ₃Cl ₄F, C ₃H ₃Cl ₃F ₂, C ₃H ₃Cl ₂F ₃, C ₃H ₃ClF ₄, C ₃H ₄Cl ₄, C ₄Cl ₄Cl ₄, C ₄Cl ₄Cl ₆, C ₄H ₅Cl ₅, C ₄H ₅Cl ₄F, and C ₅H ₄Cl ₈.

Can be under above-mentioned state, use the object lesson of the saturated halogenated hydrocarbon compound fluorination reaction that catalyst of the present invention carries out to comprise CH ₂Cl ₂Be converted into CH ₂F ₂, CHCl ₃Be converted into CHCl ₂F, CHClF ₂And CHF ₃Mixture, CH ₃CHCl ₂Be converted into CH ₃CHClF and CH ₃CHF ₂Mixture, CH ₂ClCH ₂Cl is converted into CH ₃CHClF and CH ₃CHF ₂Mixture, CH ₃CCl ₃Be converted into CH ₃CCl ₂F, CH ₃CClF ₂And CH ₃CF ₃Mixture, CH ₂ClCF ₃Be converted into CH ₂FCF ₃, CHCl ₂CF ₃Be converted into CHClFCF ₃And CHF ₂CF ₃Mixture, CHClFCF ₃Be converted into CHF ₂CF ₃, CHBrFCF ₃Be converted into CHF ₂CF ₃, CCl ₃CF ₂CCl ₃Be converted into CCl ₂FCF ₂CClF ₂And CClF ₂CF ₂CClF ₂Mixture, CCl ₃CH ₂CCl ₃Be converted into CF ₃CH ₂CF ₃, CCl ₃CH ₂CHCl ₂Be converted into CF ₃CH ₂CHF ₂, CF ₃CH=CHCl and CF ₃The mixture of CH=CHF, CF ₃CCl ₂CClF ₂Be converted into CF ₃CCl ₂CF ₃And CF ₃CClFCF ₃Mixture, CF ₃CCl ₂CF ₃Be converted into CF ₃ClFCF ₃, contain CF ₃CF ₂CHCl ₂And CClF ₂CF ₂The mixture of CHClF is converted into CF ₃CF ₂CHClF and CF ₃CF ₂CHF ₂Mixture.

Having under the situation of catalyst of the present invention, can with the formula C of HF reaction _pH _eBr _fCl _gF _hAnd C _iH _jThe example of unsaturated compound comprise C ₂Cl ₄, C ₂BrCl ₃, C ₂Cl ₃F, C ₂Cl ₂F ₂, C ₂ClF ₃, C ₂F ₄, C ₂HCl ₃, C ₂HBrCl ₂, C ₂HCl ₂F, C ₂HClF ₂, C ₂HF ₃, C ₂H ₂Cl ₂, C ₂H ₂ClF, C ₂H ₂F ₂, C ₂H ₃Cl, C ₂H ₃F, C ₂H ₄, C ₃H ₅, C ₃H ₅Cl, C ₃H ₄Cl ₂, C ₃H ₃Cl ₃, C ₃H ₂Cl ₄, C ₃HCl ₅, C ₃Cl ₆, C ₃Cl ₅F, C ₃Cl ₄F ₂, C ₃Cl ₃F ₃, C ₃Cl ₂F ₄, C ₃ClF ₅, C ₃HF ₅, C ₃H ₂F ₄, C ₃F ₆, C ₄Cl ₈, C ₄Cl ₂F ₆, C ₄ClF ₇, C ₄H ₂F ₆, and C ₄HClF ₆

Can use the object lesson of the unsaturated halogenated hydrocarbon compound fluorination reaction that catalyst of the present invention carries out to comprise CHCl=CCl ₂Be converted into CH ₂ClCF ₃And CH ₂FCF ₃Mixture, CCl ₂=CCl ₂Be converted into CHCl ₂CF ₃, CHClFCF ₃And CHF ₂CF ₃Mixture, CCl ₂=CH ₂Be converted into CH ₃CCl ₂F, CH ₃CClF ₂And CH ₃CF ₃Mixture, CH ₂=CHCl is converted into CH ₃CHClF and CH ₃CHF ₂Mixture, CF ₂=CH ₂Be converted into CH ₃CF ₃, CCl ₂=CClCF ₃Be converted into CF ₃CHClCClF ₂, CF ₃CHClCF ₃And/or CF ₃CCl=CF ₂Mixture, CF ₃CF=CF ₂Be converted into CF ₃CHFCF ₃, CF ₃CH=CF ₂Be converted into CF ₃CH ₂CF ₃, CF ₃CH=CHF is converted into CF ₃CH ₂CHF ₂

The U.S. Patent application 60/405 of application on August 22nd, 2002,223[CL2109USPRV] out of Memory about the preparation pentafluoroethane is provided, be incorporated herein by reference in full at this.

That paid close attention to is through type CHZ ₂CZ ₃Fluoridizing of halo ethane make 1,1,1,2, the 2-pentafluoroethane (is CHF ₂CF ₃Or HFC-125) catalytic process, wherein each Z is selected from F, Cl and Br, and condition is that to be no more than 4 Z are F.Preferred formula CHZ ₂CZ ₃Halo ethane comprise 2,2-two chloro-1,1,1-HFC-143a (HCFC-123) and 1,2,2-three chloro-1,1-Difluoroethane (HCFC-122).Having under the situation of catalyst of the present invention, by making CHZ ₂CZ ₃In gas phase, react and prepare HFC-125 with HF.Having under the situation of catalyst of the present invention, above-mentioned five halo ethane and HF are reflected at about 400 ℃ of about 150-, more preferably from about carry out under about 380 ℃ of the 200-.Be supplied to the amount of the HF of reactor to be at least based on CHZ ₂CZ ₃The amount of the stoichiometric proportion of Cl or the substituent number of Br in the parent material.Fluoridizing under the situation of HCFC-123, the stoichiometric proportion of HF and HCFC-123 is 2:1.Typically, HF and CHZ ₂CZ ₃The preferred proportion of parent material is that about stoichiometric proportion is to about 20:1.Be 1-60 second preferred time of contact. air form or with inert diluent such as nitrogen, helium or argon altogether streamed oxygen add with reactant, or if desired, as independent catalyst treatment.

That also need to pay close attention to is through type C ₃Cl _6-xF _xFluoridizing of six propylene halides make 2-chloro-1,1,1,3,3, the 3-HFC-236fa (is CF ₃CHClCF ₃Or HCFC-226da) catalytic process, wherein x equals 0-5.Preferred formula C ₃Cl _6-xF _xSix propylene halides comprise 1,2,2-three chloro-3,3,3-three fluoro-1-propylene (are CCl ₂=CClCF ₃Or CFC-1213xa) and hexachloropropylene (be CCl ₂=CClCCl ₃). about 400 ℃ at about 150-, under about 350 ℃ of preferably about 200-, having under the situation of catalyst of the present invention, react with HF in gas phase by above-mentioned unsaturated compound and prepare HCFC-226da.

Be supplied to the amount of the HF of reactor to be at least based on C ₃Cl _6-xF _xThe amount of the stoichiometric proportion of the substituent number meter of Cl in the parent material.Fluoridizing under the situation of CFC-1213xa, the stoichiometric proportion of HF and CFC-1213xa is 3:1.Typically, HF and C ₃Cl _6-xF _xThe preferred proportion of parent material is that about stoichiometric proportion is to about 25:1.Be 1-60 second preferred time of contact.

In gas phase fluorination, also can use the mixture of saturated halogenated hydrocarbon compound or the mixture of unsaturated hydrocarbons and/or halogenated hydrocarbon compound, and the mixture that contains unsaturated hydrocarbons and halogenated hydrocarbon compound.Can stand to use the object lesson of the mixture of the mixture of saturated halogenated hydrocarbon compound of gas phase fluorination of catalyst of the present invention and unsaturated hydrocarbons and unsaturated halogenated hydrocarbon compound to comprise CH ₂Cl ₂And CCl ₂=CCl ₂Mixture, CCl ₂FCClF ₂And CCl ₃CF ₃Mixture, CCl ₂=CCl ₂And CCl ₂=CClCCl ₃Mixture, CH ₂=CHCH ₃And CH ₂=CClCH ₃Mixture, CH ₂Cl ₂And CH ₃CCl ₃Mixture, CHF ₂CClF ₂And CHClFCF ₃Mixture, CHCl ₂CCl ₂CH ₂Cl and CCl ₃CHClCH ₂The Cl mixture, CHCl ₂CH ₂CCl ₃And CCl ₃CHClCH ₂The mixture of Cl, CHCl ₂CHClCCl ₃, CCl ₃CH ₂CCl ₃And CCl ₃CCl ₂CH ₂The mixture of Cl, CHCl ₂CH ₂CCl ₃And CCl ₃CH ₂CCl ₃Mixture, CF ₃CH ₂CCl ₂F and CF ₃CH=CCl ₂Mixture and CF ₃CH=CHCl and CF ₃CH=CCl ₂Mixture.

Chlorofluorination

The present invention includes by having under the situation of carbon monoxide-olefin polymeric, make described compound and hydrogen fluoride (HF) and chlorine (Cl ₂) reaction and improve the method for fluorine content in hydrocarbon compound or the halogenated hydrocarbon compound in gas phase, described carbon monoxide-olefin polymeric comprises that being selected from alpha-oxidation chromium that above-mentioned crystallization cobalt replaces and the described cobalt of having handled with fluorization agent replaces at least a chromium component that contains in the alpha-oxidation chromium.This carbon monoxide-olefin polymeric can randomly contain extra component such as another kind of catalysis effective metal.

The halogenated hydrocarbon compound that is suitable as chlorofluorination process parent material of the present invention can be saturated or unsaturated.The saturated halogenated hydrocarbon compound that is applicable to chlorofluorination process of the present invention comprises that general formula is C _nH _aBr _bCl _cF _dHalogenated hydrocarbon compound, wherein n is the 1-6 integer, a is the 0-12 integer, b is the 0-4 integer, c is the 0-13 integer, d is the 0-13 integer, b, c and d's and be at least l, a, b, c and d's and equal 2n+2, condition is that a+b+c is at least 1.Preferred chlorofluorination process comprises and relates to the chlorofluorination process that a wherein is at least 1 described saturated parent material.The saturated hydrocarbon compound that is applicable to chlorofluorination is to have formula C _qH _rSaturated hydrocarbon compound, wherein q is the integer of 1-6, r is 2q+2.The unsaturated halogenated hydrocarbon compound that is applicable to chlorofluorination process of the present invention comprises general formula C _pH _eBr _fCl _gF _hCompound, wherein p is the 2-6 integer, e is the 0-10 integer, f is the 0-2 integer, g is the 0-12 integer, h is the 0-11 integer, f, g and h and be at least l, e, f, g and h's and to equal the unsaturated hydrocarbon compound class that 2p. is applicable to chlorofluorination be to have formula C _iH _jHydro carbons, wherein i is the 2-6 integer, j is 2i.Can make described compound and HF and Cl by having under the situation of carbon monoxide-olefin polymeric ₂In gas phase, react and raising formula C _nH _aBr _bCl _cF _dAnd C _qH _rSaturated compounds and/or formula C _pH _eBr _fCl _gF _hAnd C _iH _jUnsaturated compound in fluorine content, described carbon monoxide-olefin polymeric comprises that being selected from alpha-oxidation chromium that above-mentioned crystallization cobalt replaces and the described cobalt of having handled with fluorization agent replaces at least a chromium component that contains in the alpha-oxidation chromium.In this article, this process is called the reaction of gas phase chlorofluorination.

The state of gas phase chlorofluorination reaction similar to above-mentioned gas phase fluorination aspect the mol ratio of temperature range, time of contact, pressure and HF and halogenated hydrocarbon compound.Be supplied to the chlorine (Cl of reactor ₂) amount whether be undersaturated and C based on the halogenated hydrocarbon compound that is supplied to reactor _nH _aBr _bCl _cF _d, C _qH _r, C _pH _eBr _fCl _gF _hAnd C _iH _jIn treat the number meter of the hydrogen that replaced by chlorine and fluorine.Make 1 mole of Cl of the saturated needs of carbon-to-carbon double bond ₂, each is needed 1 mole of Cl by the hydrogen of chlorine or fluorine replacement ₂For the reason of practice, need be just over the chlorine of stoichiometric quantity, but excessive greatly chlorine will cause the complete chlorofluorination of product.Cl ₂Be typically the about 10:1 of about 1:1-with the ratio of halogenated hydrocarbon compound.

The general formula C that can use catalyst of the present invention to carry out _nH _aBr _bCl _cF _dSaturated halogenated hydrocarbon compound and general formula C _qH _rThe object lesson of gas phase chlorofluorination reaction of saturated hydrocarbon compound comprise C ₂H ₆Be converted into and contain CH ₂ClCF ₃Mixture, CH ₂ClCF ₃Be converted into CHClFCF ₃And CHF ₂CF ₃Mixture, CCl ₃CH ₂CH ₂Cl is converted into CF ₃CCl ₂CClF ₂, CF ₃CCl ₂CF ₃, CF ₃CClFCClF ₂And CF ₃CClFCF ₃Mixture, CCl ₃CH ₂CHCl ₂Be converted into CF ₃CCl ₂CClF ₂, CF ₃CCl ₂CF ₃, CF ₃CClFCClF ₂And CF ₃CClFCF ₃Mixture, CCl ₃CHClCH ₂Cl is converted into CF ₃CCl ₂CClF ₂, CF ₃CCl ₂CF ₃, CF ₃CClFCClF ₂And CF ₃CClFCF ₃Mixture, CHCl ₂CCl ₂CH ₂Cl is converted into CF ₃CCl ₂CClF ₂, CF ₃CCl ₂CF ₃, CF ₃CClFCClF ₂And CF ₃CClFCF ₃Mixture, CCl ₃CH ₂CH ₂Cl is converted into CF ₃CCl ₂CHF ₂, CF ₃CClFCHF ₂, CF ₃CClFCClF ₂And CF ₃CClCF ₃Mixture, CCl ₃CH ₂CHCl ₂Be converted into CF ₃CCl ₂CHF ₂, CF ₃CClFCHF ₂, CF ₃CClFCClF ₂And CF ₃CCl ₂CF ₃Mixture.

The general formula C that can use catalyst of the present invention to carry out _pH _eBr _fCl _gF _hUnsaturated halogenated hydrocarbon compound and general formula C _iH _jThe object lesson of gas phase chlorofluorination reaction of unsaturated hydrocarbon compound comprise C ₂H ₄Be converted into CCl ₃CClF ₂, CCl ₂FCCl ₂F, CClF ₂CCl ₂F, CCl ₃CF ₃, CF ₃CCl ₂F and CClF ₂CClF ₂Mixture, C ₂Cl ₄Be converted into CCl ₃CClF ₂, CCl ₂FCCl ₂F, CClF ₂CCl ₂F, CCl ₃CF ₃, CF ₃CCl ₂F and CClF ₂CClF ₂Mixture, C ₃H ₆Or CF ₃CCl=CCl ₂Be converted into CF ₃CCl ₂CClF ₂, CF ₃CCl ₂CF ₃, CF ₃CClFCClF ₂And CF ₃CClFCF ₃Mixture.

What pay close attention to is to have under the situation of catalyst of the present invention, by making ethane and HF and Cl ₂Reaction is made and is contained 2-

chlorine

1,1 in gas phase, and the 1-HFC-143a (is CH ₂ClCF ₃The catalytic process of mixture or HCFC-133a). about 400 ℃ at about 150-of the chlorofluorinations of ethane, more preferably from about carry out under about 400 ℃ of the 300-.The mol ratio of HF and ethane is preferably the about 15:1 of about 3:1-, chlorine is preferably with the mol ratio of ethane and is about 2:1-5:1. preferred time of contact about 60 seconds of about 5-. air form or add with reactant with the common streamed oxygen of inert diluent such as nitrogen, helium or argon, or if desired, as independent catalyst treatment.

That paid close attention to is through type C ₃Cl _6-xF _xThe chlorofluorination of six propylene halides make 1,2,2-three chloro-1,1,3,3, the 3-pentafluoropropane (is CClF ₂CCl ₂CF ₃Or CFC-215aa), 2,2-two chloro-1,1,1,3, the 3-pentafluoropropane (is CF ₃CCl ₂CF ₃Or CFC-216aa), 1,2-two chloro-1,1,1,3,3, the 3-HFC-236fa (is CClF ₂CClFCF ₃Or CFC-216ba) and 2-chloro-1,1,1,2,3,3, the 3-heptafluoro-propane (is CF ₃CClFCF ₃The catalytic process of mixture or CFC-217ba), wherein x equals the preferred formula C of 0-4. ₃Cl _6-xF _xSix propylene halides comprise 1,2,2-three chloro-3,3,3-three fluoro-1-propylene (are CCl ₂=CClCF ₃Or CFC-1213xa) and hexachloropropylene (be CCl ₂=CClCCl ₃).At about 150-about 450 ℃, under preferably about 250-400 ℃, having under the situation of catalyst of the present invention, by above-mentioned unsaturated compound in gas phase with Cl ₂With HF react prepare CFC-215aa ,-216aa ,-216ba and-mixture of 217ba.

Be supplied to the amount of the HF of reactor to be at least based on C ₃Cl _6-xF _xSubstituent number of Cl and required end product are formed the amount of the stoichiometric proportion of meter in the parent material.Under the situation of mixture that with the CFC-1213xa chlorofluorination for fluoro substituents average is 6 chlorine fluorine propane, the stoichiometric proportion of HF and CFC-1213xa is 3:1.Typically, HF and C ₃Cl _6-xF _xThe preferred proportion of parent material is that stoichiometric proportion is to about 30:1, more preferably from about 8:1-25:1.

Be supplied to the amount of the chlorine of reactor should be at least the amount of stoichiometric proportion.Cl ₂With the preferred molar ratio of CFC-1213xa be the about 5:1 of about 1:1-.

Be about 60 seconds of about 5-preferred time of contact.

At the U.S. Patent application US 60/405 of on August 22nd, 2002 application, 222[CL2108US PRV] in other data of the chlorofluorination of CFC-1213xa is provided, quote it herein in full as a reference.

Use catalyst of the present invention and to contain saturated and mixture chlorofluorination unsaturated compound with the mixture of mixture, unsaturated hydrocarbon compound and the unsaturated halogenated hydrocarbon compound of saturated hydrocarbon compound and saturated halogenated hydrocarbon compound.The object lesson of the mixture of operable saturated and unsaturated hydrocarbons and halogenated hydrocarbons comprises CCl ₂=CCl ₂And CCl ₂=CClCCl ₃Mixture, CHCl ₂CCl ₂CH ₂Cl and CCl ₃CHClCH ₂The mixture of Cl, CHCl ₂CH ₂CCl ₃And CCl ₃CHClCH ₂The mixture of Cl, CHCl ₂CHClCCl ₃, CCl ₃CH ₂CCl ₃And CCl ₃CCl ₂CH ₂The mixture of Cl, CHF ₂CH ₂CF ₃And CHCl=CHCF ₃Mixture and CH ₂=CH ₂And CH ₂=CHCH ₃Mixture.

Isomerization and disproportionation

The present invention includes by the described halogenated hydrocarbon compound of isomerization changes the method that fluorine distributes under the situation of carbon monoxide-olefin polymeric in this halogenated hydrocarbon compound having, described carbon monoxide-olefin polymeric comprises that being selected from alpha-oxidation chromium that above-mentioned crystallization cobalt replaces and the described cobalt of having handled with fluorization agent replaces at least a chromium component that contains in the alpha-oxidation chromium.

The present invention also comprises by the described halogenated hydrocarbon compound of disproportionation changes the method that fluorine distributes in this halogenated hydrocarbon compound in gas phase having under the situation of carbon monoxide-olefin polymeric, and described carbon monoxide-olefin polymeric comprises that being selected from alpha-oxidation chromium that above-mentioned crystallization cobalt replaces and the described cobalt of having handled with fluorization agent replaces at least a chromium component that contains in the alpha-oxidation chromium.

The halogenated hydrocarbon compound that is suitable as isomerization of the present invention and dismutation parent material can be saturated or unsaturated. the saturated halogenated hydrocarbon compound that is applicable to isomerization of the present invention and dismutation comprises general formula C _nH _aBr _bCl _cF _dHalogenated hydrocarbon compound, wherein n is the 2-6 integer, a is the 0-12 integer, b is the 0-4 integer, and c is the 0-13 integer, and d is the 1-13 integer, a, b, c and d's and equal 2n+2, condition is that a+b+c is at least 1. and is applicable to that the undersaturated halogenated hydrocarbon compound of isomerization of the present invention and dismutation comprises general formula C _pH _eBr _fCl _gF _hHalogenated hydrocarbon compound, wherein p is the 2-6 integer, e is the 0-10 integer, f is the 0-2 integer, g is the 0-12 integer, h is the 1-11 integer, e, f, g and h's and equal 2p, condition is e, f and g's and be at least 1.

In one embodiment of the invention, by resetting H, Br, Cl and F substituting group in the molecule (typically resetting to preferably arranging on the thermodynamics), the fluorine that keeps equal number H, Br, Cl and F substituting group to change halogenated hydrocarbon compound simultaneously respectively distributes.Claim that in this article this process is isomerization.

In another embodiment of the invention, one or morely compare halogenated hydrocarbons that fluorine content reduces with the halogenated hydrocarbons parent material and compare the fluorine that halogenated hydrocarbon compounds that fluorine content improves change halogenated hydrocarbon compound with the halogenated hydrocarbons parent material and distribute to form with one or more by at least one H, Br in another molecule of at least one the F substituting group in the molecule that makes the halogenated hydrocarbons parent material and halogenated hydrocarbons parent material and/or the exchange of Cl substituting group.Claim that in this article this process is a disproportionation.

In another embodiment of the invention, isomerization and disproportionated reaction can occur simultaneously.

No matter implement isomerization, disproportionation or isomerization and disproportionation, can change formula C under the situation of carbon monoxide-olefin polymeric arranged _nH _aBr _bCl _cF _dSaturated compounds and/or formula C _pH _eBr _fCl _gF _hThe fluorine of unsaturated compound distribute, described carbon monoxide-olefin polymeric comprises that being selected from alpha-oxidation chromium that above-mentioned crystallization cobalt replaces and the described cobalt of having handled with fluorization agent replaces at least a chromium component that contains in the alpha-oxidation chromium.

Typically, at about 150-500 ℃, carry out isomerization and disproportionated reaction under about 400 ℃ of preferably about 200-. typically, be about 120 seconds of about 1-, about 60 seconds of preferably about 5-time of contact in the reactor.Can under the situation that inert gas such as helium, hydrogen or nitrogen are arranged, carry out isomerization and disproportionated reaction, although this is not preferred. can carry out isomerization and disproportionated reaction under the situation that HF and HCl are arranged, this is not preferred.

The object lesson that the gas phase isomerization that can use catalyst of the present invention to carry out reacts comprises CClF ₂CCl ₂F is converted into CCl ₃CF ₃, CClF ₂CClF ₂Be converted into CF ₃CCl ₂F, CHF ₂CClF ₂Be converted into CF ₃CHClF, CHF ₂CHF ₂Be converted into CF ₃CH ₂F, CF ₃CClFCClF ₂Be converted into CF ₃CCl ₂CF ₃, CF ₃CHFCHF ₂Be converted into CF ₃CH ₂CF ₃

Can use the object lesson of the gas phase disproportionated reaction that catalyst of the present invention carries out to comprise CClF ₂CClF ₂Be converted into CClF ₂CCl ₂F, CCl ₃CF ₃And CF ₃CClF ₂Mixture, CHClFCF ₃Be converted into CHCl ₂CF ₃And CHF ₂CF ₃Mixture.

What paid close attention to is 2-chloro-1,1,2, and the 2-HFC-134a (is CHF ₂CClF ₂Or HCFC-124a) and 2-chloro-1,1,1, the 2-HFC-134a (is CF ₃CHClF or HCFC-124) mixture be converted into except the parent material that does not change and also contain 2,2-two chloro-1,1, the 1-HFC-143a (is CHCl ₂CF ₃Or HCFC-123) and 1,1,1,2, the 2-pentafluoroethane (is CF ₃CHF ₂The process of mixture or HFC-125). under the optional situation about existing of the diluent in being selected from HF, HCl, nitrogen, helium, argon and carbon dioxide, contact with catalyst of the present invention with-124 mixture and in gas phase, obtain to contain the mixture of HFC-125 and HCFC-123 by HCFC-124a. preferably about 400 ℃ at about 150-, if more preferably from about carry out disproportionation under about 350 ℃ of the 250-. use, then carrier gas can serve as that the mol ratio of the about 5:1 of about 1:1-exists with diluent and halo ethane. preferably be about 60 seconds of about 10-time of contact.

Dehydrofluorination

The present invention includes by having under the situation of carbon monoxide-olefin polymeric, make described halogenated hydrocarbon compound dehydrofluorination and reduce the method for fluorine content in the halogenated hydrocarbons, described carbon monoxide-olefin polymeric comprises that being selected from alpha-oxidation chromium that above-mentioned crystallization cobalt replaces and the described cobalt of having handled with fluorization agent replaces at least a chromium component that contains in the α chromium oxide.

The halogenated hydrocarbon compound that is suitable as dehydrofluorination process parent material of the present invention is saturated typically.The saturated halogenated hydrocarbon compound that is applicable to dehydrofluorination process of the present invention comprises general formula C _nH _aF _dCompound, wherein n is the 2-6 integer, a is the 1-12 integer, d is the 1-13 integer, a and d and equal 2n+2.Can reduce formula C having under the situation of carbon monoxide-olefin polymeric _nH _aF _dSaturated compounds in fluorine content, described carbon monoxide-olefin polymeric comprises that being selected from alpha-oxidation chromium that above-mentioned crystallization cobalt replaces and the described cobalt of having handled with fluorization agent replaces at least a chromium component that contains in the alpha-oxidation chromium. the reduction of this fluorine content typically with to remove hydrogen fluoride (HF) from molecule relevant, is referred to as dehydrofluorination in this article.

Typically, about 500 ℃ at about 200-, carry out dehydrofluorination under about 450 ℃ of preferably about 300-.Typically, be about 360 seconds of about 1-time of contact in the reactor, about 120 seconds of preferably about 5-.Implement the decomposition that dehydrofluorination promotes the fluorinated hydrocarbons compound under the situation that inert gas such as helium, hydrogen or nitrogen are arranged, but this practice also can cause separation difficulty, be not preferred therefore.

The product of dehydrofluorination is by HF and lose the unsaturated fluorinated hydrocarbons compound that HF produces by parent material and form.The object lesson that the gas phase dehydrofluorination that can use catalyst of the present invention to carry out is reacted comprises CH ₃CHF ₂Be converted into CH ₂=CHF, CH ₃CF ₃Be converted into CH ₂=CF ₂, CF ₃CH ₂F is converted into CF ₂=CHF, CHF ₂CH ₂CF ₃Be converted into CHF=CHCF ₃, CF ₃CH ₂CF ₃Be converted into CF ₃CH=CF ₂

What paid close attention to is by 1, and the 1-Difluoroethane (is CHF ₂CH ₃Or HFC-152a) it (is CH that dehydrofluorination is made fluorinated ethylene (fluoroethene) ₂=CHF or vinyl are fluoridized thing) catalytic process.Under the optional situation about existing of diluent in being selected from HF, nitrogen, helium, argon and carbon dioxide, the mixture of the HFC-152a that can in gas phase, obtain to contain PVF by HFC-152a is contacted with catalyst of the present invention and not change. preferably, at about 150-about 400 ℃, more preferably from about carry out dehydrofluorination under about 350 ℃ of the 250-.If use, then carrier gas can serve as that the mol ratio of the about 5:1 of about 1:1-exists with diluent and halo ethane.Be about 60 seconds of about 10-preferred time of contact.

The chlorination defluorinateization

The present invention includes by having under the situation of carbon monoxide-olefin polymeric, described halogenated hydrocarbons and hydrogen chloride (HCl) are reacted in gas phase and reduce the method for fluorine content in the halogenated hydrocarbon compound, described carbon monoxide-olefin polymeric comprises that being selected from alpha-oxidation chromium that above-mentioned crystallization cobalt replaces and the described cobalt of having handled with fluorization agent replaces at least a chromium component that contains in the alpha-oxidation chromium.

The halogenated hydrocarbon compound that is suitable as chlorination defluorinate process parent material of the present invention can be saturated or unsaturated.The saturated halogenated hydrocarbon compound that is applicable to chlorination defluorinate process of the present invention comprises that general formula is C _nH _aCl _cF _dHalogenated hydrocarbon compound, wherein n is the 1-6 integer, a is the 0-12 integer, c is the 0-13 integer, d is the 1-13 integer, a, c and d's and equal the undersaturated halogenated hydrocarbon compound that 2n+2. is applicable to chlorination defluorinate process of the present invention and comprise general formula C _pH _eCl _gF _hHalogenated hydrocarbon compound, wherein p is the 2-6 integer, e is the 0-10 integer, g is the 0-12 integer, h is the 1-11 integer, e, f and h's and equal 2p.Can be by having under the situation of carbon monoxide-olefin polymeric, described compound and HCl are reacted in gas phase and reduce formula C _nH _aCl _cF _dSaturated compounds and formula C _pH _eCl _gF _hUnsaturated compound in fluorine content, described carbon monoxide-olefin polymeric comprises that being selected from alpha-oxidation chromium that above-mentioned crystallization cobalt replaces and the described cobalt of having handled with fluorization agent replaces at least a chromium component that contains in the alpha-oxidation chromium.In this article, this process is called gas phase chlorination defluorinate reaction.In U.S. Pat 5,345, the chlorination defluorinateization is disclosed in 017 and US5,763,698, the instruction that is incorporated herein these two patents herein is as a reference.

Typically, at about 250-450 ℃, carry out chlorination defluorinate reaction under about 400 ℃ of preferably about 300-.Typically, be about 120 seconds of about 1-time of contact in the reactor, about 60 seconds of preferably about 5-.Most convenient ground carries out this reaction under atmospheric pressure or super-atmospheric pressure.

The chlorination defluorinateization of being paid close attention to especially that relates to saturated halogenated hydrocarbon.The mol ratio of HCl and saturated halogenated hydrocarbon compound is typically the about 100:1 of about 1:1-, the about 50:1 of preferably about 3:1-, the most preferably from about about 30:1 of 4:1-.Generally speaking, for given carbon monoxide-olefin polymeric, temperature is high more, time of contact is long more, the mol ratio of HCl and saturated halogenated hydrocarbon compound is big more, and it is just big more to be converted into the lower conversion of compounds rate of fluorine content.Above-mentioned variable can balance each other, thereby makes the formation maximum of the product of chlorine replacement.

The product typical case of chlorination defluorinate reaction comprises unreacted HCl, HF, the parent material that does not change and makes fluorine content compared with the low saturated halogenated hydrocarbon compound of material that begins because one or more fluorine are replaced by chlorine. can use the object lesson of the gaseous oxidation defluorinate reaction that catalyst of the present invention carries out to comprise CHF ₃Be converted into CHCl ₃, CHCl ₂F and CHClF ₂Mixture, CClF ₂CClF ₂Be converted into CCl ₃CCl ₃, CCl ₃CCl ₂F, CCl ₃CClF ₂, CCl ₂FCCl ₂F, CClF ₂CCl ₂F and CCl ₃CF ₃Mixture, CF ₃CClF ₂Be converted into CCl ₃CCl ₃, CCl ₃CCl ₂F, CCl ₃CClF ₂, CCl ₂FCCl ₂F, CClF ₂CCl ₂F, CCl ₃CF ₃, CClF ₂CClF ₂And CF ₃CCl ₂The mixture of F, CF ₃CCl ₂CF ₃Be converted into CF ₃CCl ₂CClF ₂, CF ₃CCl ₂CCl ₂F, CF ₃CCl ₂CCl ₃And CClF ₂CCl ₂CCl ₃Mixture, CF ₃CH ₂CF ₃Be converted into CCl ₂=CHCF ₃And CCl ₂=CClCF ₃Mixture.

What paid close attention to is to have under the situation of catalyst of the present invention, and by 1,1,1,3,3, the 3-HFC-236fa (is CF by HFC-236fa and HCl are reacted in gas phase ₃CH ₂CF ₃Or HFC-236fa) chlorination defluorinate manufacturing contains 1,1-two chloro-3,3, and 3-three fluoro-1-propylene (are CCl ₂=CHCF ₃Or HCFC-1223za) and 1,1,2-three chloro-3,3,3-three fluoro-1-propylene (are CCl ₂=CClCF ₃The catalytic process of mixture or CFC-1213xa). preferably about 450 ℃ of this reactions at about 275-, more preferably from about carry out under about 400 ℃ of the 300-, and the mol ratio of HCl and HFC-236fa to be preferably the about 20:1. of about 3:1-preferred time of contact be about 40 seconds of about 1-.Air form or with inert diluent such as nitrogen, helium or argon altogether streamed oxygen add with reactant, or if desired, as independent catalyst treatment.

Technology that can be by routine as include but not limited to wash, the combination of decant or distillation separates the product that process of the present invention obtains. some products of different embodiments of the present invention can form one or more azeotropic mixtures each other or with HF.

Can use well-known Chemical Engineering practice easily to implement process of the present invention.

Use

Has the desired properties that is used for direct commercial use by the partial reaction product that uses catalyst disclosed herein to obtain.For example, find CH ₂F ₂(HFC-32), CHF ₂CF ₃(HFC-125), CHF ₂CF ₃(HFC-125), CH ₂FCHF ₂(HFC-134), CF ₃CH ₂CF ₃(HFC-236fa) and CF ₃CH ₂CHF ₂(HFC-245fa) as the application of refrigerant, find CH ₂FCF ₃(HFC-134a) and CF ₃CHFCF ₃HFC-227ea) as the application of propellant, find CH ₂FCHF ₂(HFC-134) and CF ₃CH ₂CHF ₂(HFC-245fa) as the application of blowing agent, find CHF ₂CF ₃(HFC-125), CF ₃CH ₂CF ₃(HFC-236fa) and CF ₃CHFCF ₃(HFC-227ea) as the application of extinguishing chemical.

Other product of using the application of the invention acquisition is as the chemical intermediate of making useful product.For example, can be with CCl ₃CF ₃(CFC-113a) be used for preparation and can change CH into by hydrogenation dechlorination (hydrodechlorination) then ₂FCF ₃(HFC-134a) CFC-114a.Similarly, can be by the hydrogenation dechlorination with CF ₃CCl ₂CF ₃(CFC-216aa) be used to prepare CF ₃CH ₂CF ₃(HFC-236fa), can be by hydrogenation with CF ₃CCl=CF ₂(CFC-1215zc) be used to prepare CF ₃CH ₂CHF ₂(HFC-245fa).

We think, use description herein, those of ordinary skills need not further study intensively the degree that just the present invention can be applied to its fullest. and therefore, following specific embodiment being interpreted as just illustrative, in no case is to retrain all the other disclosures by any way.

Embodiment

Catalyst characterization

The energy branch is penetrated spectroscopy (EDS) and transmission electron microscope art (TEM)

In these researchs, the Philips CM-20 high resolution transmission electron microscope analyzing crystal that uses operation under the accelerating potential of 200kV, outfit to have the windowless BDS of the Oxford system of Si (Li) element detector.In EDS analyzes, electron lucent thin slice with sample makes thickness of sample effect such as fluorescence minimum. and, because the atomic weight of Cr, Co and Ni is similar, so supposing their X-radiation absorption cross section is identically (to see that Zaluzec is at J.J.Hren, J.I.Goldstein and D.C.Joy (Plenum Press, New York, 1979) argumentation of the 121-167 page or leaf of editor's Introduction to Analytical Electron Microscopy).The existence of copper is because due to the TEM grid and background in the microscope among Fig. 1,2 and 3 the EDS.

X-x ray absorption spectrum x (XAS) and X-ray powder diffraction (XRD)

The method of describing in X-ray diffraction (Addison-Wesley, Reading, MA, 1969) according to Warren obtains and Analysis of X RD data.At Advanced Photon Source, beamline5BMD, the DND-CAT of Argonne National Laboratory obtain the XAS data.Use Koningsberger and Prins at X-ray Absorption:Principles, Applications, Techniques of EXAFS, SEXAFS and XANES (John Wiley﹠amp; Sons, New York, 1988) middle method acquisition and the Analysis of X AS data of describing.Obtained the spectrum on the K limit (edges) of Cr, Co and Ni. in how much of transmissions (transmission geometry), obtain the Cr limit, and because the concentration of Co and Ni is low, so under fluorescence mode, obtain Co and Ni limit.

The overall average of the whole Co atoms of the data representation in the table 2. ligancy is to infer from the radial distribution function of the Fourier transformation acquisition in the extended X-ray absorption fine structure of Co spectrum (EXAFS) zone. oxidation state is by sample near side (ns) Co spectrum and the standard sample match with known oxidation state are obtained.

Use Advanced Photon Source acquisition XRD and XAS data to obtain USDepartment of Energy, the support of Office of Basic Energy Sciences, contract number W-31-109-Eng-38.

Preparation of Catalyst

Comparative preparation embodiment 1

Prepare 100% chrome catalysts (400 ℃)

With 477mL7.4M WITH AMMONIA TREATMENT 400g Cr (NO ₃) ₃[9 (H ₂O)] (1.0 moles) solution in the 1000mL deionized water is increased to about 8.5 with the pH value.At room temperature stir one night of this slurry.After with ammoniacal liquor the pH value being adjusted to 8.5 again, this mixture is poured in the evaporating dish, and under 120 ℃, air drying. then, the solid that calcination obtains under 400 ℃, in the air 24 hours.

Studied 100% chromium oxide by TEM and EDS.Product is by the even α-Cr with the narrow particle size range of about 20nm ₂O ₃Crystal is formed.EDS shows and has chromium and oxygen do not have pollutant.

Preparation embodiment 2

Prepare 99% chromium/1% Co catalysts (400 ℃)

Preparation 792.29g Cr (NO ₃) ₃[9 (H ₂O)] (1.98 moles) and 5.82gCo (NO ₃) ₂[6 (H ₂O)] (0.0200 mole) solution in the 2000mL deionized water. drip this solution of processing with 955mL7.4M ammoniacal liquor, this is increased to about 8.5 with the pH value.At room temperature stir one night of this slurry. the pH value was adjusted to 8.5 in second day.Then, use two glass funnels (fritted funnel) to collect solid; Rise deionized water with 15-20 and wash the solid that obtains in each funnel. under 120 ℃, this solid of air drying 24 hours, then under 400 ℃, calcination 24 hours in the air.

Show that by TEM and EDS analytic sample existence is of a size of α-Cr of 20-40nm ₂O ₃Crystal.Cobalt is present in the chromium oxide lattice.

Preparation embodiment 3

Prepare 98% chromium/2% Co catalysts (400 ℃)

Preparation 784.30gCr (NO ₃) ₃[9 (H ₂O)] (1.96 moles) and 11.64gCo (NO ₃) ₂[6 (H ₂O)] (0.040 mole) solution in the 2000mL deionized water.Drip to handle this solution with 950mL7.4M ammoniacal liquor, this is increased to about 8.5. with the pH value from about 1.8 and at room temperature stirs one night of slurry, then in air, 110-120 ℃ following evaporate to dryness 48 hours.The catalyst of drying is divided into two halves.Half calcination 24 hours under 400 ℃, in the air.

Studied the Cr/Co oxide by TEM and EDS. oxide is made up of the crystal of 20-40nm.EDS shows that cobalt is at whole α-Cr ₂O ₃Evenly distribute in the structure.Confirm that by XRD and XAS analytic sample crystal has α-Cr ₂O ₃Structure, the average oxidation state of cobalt is 2.94.Mix α-Cr ₂O ₃The amount of cobalt is 1.7-2.0 atom % in the lattice.

Preparation embodiment 4

Prepare 98% chromium/2% Co catalysts (900 ℃)

In air, 900 ℃ of following calcination prepare second half dry catalyst 24 hours of preparation among the embodiment 3.

Preparation embodiment 5

Prepare 98% chromium/2% Co catalysts (400 ℃)

Preparation 784.29g Cr (NO ₃) ₃[9 (H ₂O)] (1.96 moles) and 11.64gCo (NO ₃) ₂[6 (H ₂O)] (0.040 mole) solution in the 2000mL deionized water.Drip this solution of processing with 950mL7.4M ammoniacal liquor and reach about 8.5 until the pH value.At room temperature stirred this slurry 24 hours, and made the pH value remain on 8.5 simultaneously.Then, in air, 110-120 ℃ this slurry of following evaporate to dryness, simultaneously 120 ℃ of following heating and continuous weeks. then, the calcination dry catalyst is 24 hours under 400 ℃, in the air.

Preparation embodiment 6

Prepare 98% chromium/2% Co catalysts (550 ℃)

Preparation 1.010g Cr (NO ₃) ₃[9 (H ₂O)] (2.52 moles) and 14.6gCo (NO ₃) ₂[6 (H ₂O)] (0.050 mole) solution in the 1000mL deionized water. evaporate this green solution down until forming the aterrimus precipitation at about 100 ℃. on heating plate, in 300-325 ℃ of following drying solid.Then, in porcelain dish, calcination is 20 hours in 550 ℃ kiln with this solid transfer.

Show the α-Cr that exists cobalt to replace by TEM and EDS analytic sample ₂O ₃Crystal, simultaneously because calcining heat is higher, particle diameter has only less increase.Compare with observed 10-30nm in the sample that is 400 ℃ of following calcination, the particle diameter of spinelle phase is increased to about 20-50nm.

Preparation embodiment 7

Prepare 98% chromium/2% Co catalysts (400 ℃)

With Cr (NO ₃) ₃[9 (H ₂O)] (50.5g, 0.126 mole) and Co (NO ₃) ₂[6 (H ₂O)] (0.73g, 0.00251 mole) is weighed in the porcelain crucible, and in air, when stirring they is melted to together.This mixture is heated to decomposition, calcination 24 hours in 400 ℃ kiln then.

Show that by TEM and EDS analytic sample the cobalt that has 100-150nm replaces α-Cr ₂O ₃Crystal and a large amount of relatively particle diameters are the spinelle phase of about 10-30nm.

With to top similar mode, preparation also always consists of the cobalt/chromated oxide composition of 0.5 atom % cobalt/99.5 atom % chromium, 1.0 atom % cobalts/99 atom % chromium, 3 atom % cobalts/97 atom % chromium and 4 atom % cobalts/96 atom % chromium 400 ℃ of following calcination.

The thermogravimetric analysis of this 5 cobalts/chromium composition shows that calcining causes nitrate precursor incomplete decomposing under 400 ℃.These 5 composition sample of calcination 12 hours again under 550 ℃.Analyze these samples by XAS and show, the average oxidation state of cobalt is+3.0-+3.2.For XAS research, nominally contain 0.5 atom % cobalt sample cobalt very little. the average oxidation state of chromium is+3.2; Also exist and contain a small amount of Cr ^{+ 6}Phase .XRD and XAS data show, be present in α-Cr with it around the partial structurtes of cobalt ₂O ₃Consistent in the lattice.Also there is the second very little phase of particle diameter, thinks that it is CrCoO ₃.

Preparation embodiment 8

Prepare 97.8% chromium/2.2% Co catalysts (550 ℃)

With Cr (NO ₃) ₃[9 (H ₂O)] (50.33g, 0.126 mole) and Co (NO ₃) ₂[6 (H ₂O)] (0.82g, 0.00282 mole) is weighed in the porcelain crucible, and in air, when stirring they is melted to together. this mixture is heated to decomposition, calcination 12 hours in 550 ℃ kiln then.

With to top similar mode, preparation also always consists of the cobalt/chromated oxide composition of 2.4 atom % cobalts/97.6 atom % chromium and 2.7 atom % cobalts/97.3 atom % chromium 550 ℃ of following calcination.

To analyze these 3 samples by XAS and show, the average oxidation state of cobalt is+the average oxidation state+3.13-+3.20 of 3.1-+3.2. chromium, also exist simultaneously and contain a small amount of Cr ^{+ 6}Phase.XRD and XAS data show that the partial structurtes that center on cobalt are present in α-Cr with it ₂O ₃Consistent in the lattice. also there is the second very little phase of particle diameter, thinks that it is CrCoO ₃

Preparation embodiment 9

Prepare 98% chromium/2% Co catalysts (550 ℃)

Preparation 1,010g Cr (NO ₃) ₃[9 (H ₂O)] (2.52 moles) and 14.6gCo (NO ₃) ₂[6 (H ₂O)] (0.0502 mole) solution in the 1500mL deionized water.This solution of WITH AMMONIA TREATMENT with 500mL29 weight % mixes by mechanical agitator simultaneously. and stirred this mixture 2 hours, the pH value stabilization is transferred to mixture in the big ceramic ware at 6.0..Drive away water by heating.After evaporating most of water, on heating plate, sample is heated to 250-300 ℃. then, in porcelain dish, calcination is 20 hours in 550 ℃ kiln with the solid transfer that obtains.

Show by TEM and EDS analytic sample, mutually minimum by the spinelle that the precipitation method form. about 90% cobalt replaces α-Cr ₂O ₃Be made up of the crystal that is of a size of 20-40nm, remaining 10% is the very large crystal that is of a size of 200-400nm.

Preparation embodiment 10

Prepare 97% chromium/3% Co catalysts (not washing, 400 ℃)

Preparation 776.29g Cr (NO ₃) ₃[9 (H ₂O)] (1.94 moles) and 17.46gCo (NO ₃) ₂[6 (H ₂O)] (0.060 mole) solution in the 2000mL deionized water.Drip to handle this solution with 950mL 7.4M ammoniacal liquor and reach about 8.5. until the pH value and at room temperature stirred slurry 24 hours, then in air, 110-120 ℃ following evaporate to dryness.With the catalyst grind into powder of drying, then in air, 400 ℃ of following calcination 24 hours. the surface area of calcined product is 30.5m ²/ g.

Preparation embodiment 11

Prepare (the washing of 97% chromium/3% Co catalysts; 400 ℃)

Preparation 776.29g Cr (NO ₃) ₃[9 (H ₂O)] (1.94 moles) and 17.46gCo (NO ₃) ₂[6 (H ₂O)] (0.060 mole) solution in the 2000mL deionized water. drip this solution of processing with 955mL7.4M ammoniacal liquor, this is increased to about 8.5 with the pH value.At room temperature stir one night of this slurry, and the pH value is adjusted to 8.5 at second day.In 2 3L glass funnels, each several part is with the washing of 15-20L deionized water with solid collection. then, this washed solid of evaporate to dryness is 24 hours under 120 ℃, in the air, then under 400 ℃, calcination 24 hours in the air.The surface area of calcined product is 17.8m ²/ g.

Studied the Cr/Co oxide by TEM and EDS.α-Cr ₂O ₃Crystal by 100nm is formed, and EDS shows the cobalt that exists replacement to enter lattice.This sample also contains second phase of being made up of the 10nm crystal.EDS shows, but this contains the cobalt and the chromium of comparative quantity mutually, may be the spinelle phase.

Preparation embodiment 12

Prepare 95% chromium/5% Co catalysts (900 ℃)

Preparation 380.14g Cr (NO ₃) ₃[9 (H ₂O)] (0.95 mole) and 14.55gCo (NO ₃) ₂[6 (H ₂O)] (0.050 mole) solution in the 1000mL deionized water. drip this solution of processing with 450mL7.4M ammoniacal liquor, the pH value is increased to 8.4 from about 1.7 simultaneously.At room temperature stir one night of slurry, then in air, 120 ℃ of following evaporates to dryness, and remain on this temperature next night.With the catalyst grind into powder of drying, then in air, 900 ℃ of following calcination 20 hours.

Preparation embodiment 13

Prepare 95% chromium/5% Co catalysts (400 ℃)

Preparation 760.28g Cr (NO ₃) ₃[9 (H ₂O)] (1.90 moles) and 29.10gCo (NO ₃) ₂[6 (H ₂O)] (0.10 mole) solution in the 2000mL deionized water.Drip to handle this solution with 950mL 7.4M ammoniacal liquor, this is increased to about 8.5. with the pH value and at room temperature stirs one night of slurry, then in air, 110-120 ℃ following evaporate to dryness 48 hours. with the catalyst of drying in two.Half calcination 24 hours under 400 ℃, in the air.The surface area of calcined product is 33.6m ²/ g.

Studied the Cr/Co95/5 oxide by TEM and EDS. α-Cr ₂O ₃Crystal by 50nm is formed, and EDS shows the cobalt that exists replacement to enter lattice.This sample also contains the small crystals of spinelle phase.Confirm that by XRD and XAS analytic sample crystal has α-Cr ₂O ₃Structure, the average oxidation state of cobalt is 2.84.Mix α-Cr ₂O ₃The amount of cobalt is 3.8-4.4 atom % in the lattice.

Preparation embodiment 14

Prepare 95% chromium/5% Co catalysts (900 ℃)

In air, 900 ℃ of following calcination prepare second half dry catalyst 24 hours of preparation among the embodiment 13.

Preparation embodiment 15

Prepare 95% chromium/5% Co catalysts (excessive NH of 1.5 equivalents ₄NO ₃, 400 ℃)

Preparation 760.28g Cr (NO ₃) ₃[9 (H ₂O)] (1.90 moles) and 29.10gCo (NO ₃) ₂[6 (H ₂O)] (0.10 mole) solution in the 2000mL deionized water. drip this solution of processing with 950mL7.4M ammoniacal liquor; The pH value reaches 8.5.At room temperature stir this slurry 24 hours, and used 240.12g NH then ₄NO ₃The solution-treated of (3.0 moles).After at room temperature stirring 2 hours, in air, 120 ℃ of these mixtures of following evaporate to dryness, and remain on next week of this temperature.With mortar and tamper catalyst grind into powder with drying, then in air, 400 ℃ of following calcination 24 hours.The surface area of calcined product is 36.5m ²/ g.

Preparation embodiment 16

Prepare (the washing of 90% chromium/10% Co catalysts; 400 ℃)

Preparation 720.27gCr (NO ₃) ₃[9 (H ₂O)] (1.80 moles) and 58.21gCo (NO ₃) ₂[6 (H ₂O)] (0.20 mole) solution in the 2000mL deionized water. drip this solution of processing with 955mL 7.4M ammoniacal liquor, this is increased to about 8.5 with the pH value from about 2.1.At room temperature stir one night of this slurry. second day, by adding ammoniacal liquor with the pH value from 8.05 be increased to 8.5. with solid collection 2 3L glass funnels, each several part is with the washing of 15-20L deionized water. then, and the solid of evaporate to dryness washing under 120 ℃, in the air 24 hours.Then, under 400 ℃, calcination dry catalyst 24 hours in the air.

Studied the Cr/Co90/10 oxide by TEM and EDS.Sample is by two phase compositions.α-Cr ₂O ₃Crystal by 100nm is formed, and EDS shows that cobalt is present in the lattice.This sample also contains spinel-like phase a large amount of relatively, the 10nm crystal form. show that by XRD and XAS analytic sample sample is mainly α-Cr ₂O ₃Structure, the average oxidation state of cobalt are that 2.63. mixes α-Cr ₂O ₃The amount of cobalt is 4.5-5.9 atom %. in the lattice

Preparation embodiment 17

Prepare 90% chromium/10% Co catalysts (excessive NH of 3.3 equivalents ₄NO ₃400 ℃)

Preparation 72.03g Cr (NO ₃) ₃[9 (H ₂O)] (0.18 mole) and 5.82gCo (NO ₃) ₂[6 (H ₂O)] (0.020 mole) solution in the 200mL deionized water.Make the pH value of solution reach 8.5 with the 7.4M WITH AMMONIA TREATMENT.At room temperature stirred this slurry 24 hours. then, with the 48.02gNH that is dissolved in the 100mL water ₄NO ₃This mixture of solution-treated of (0.60 mole). stirred this slurry 1 hour, then under 120 ℃, about 90 hours of air drying.The solid of drying is ground into powder, puts into the ware of covering then, and calcination 24 hours under 400 ℃, in the air.

Show primary crystallization phase α-Cr by the XRD analysis sample ₂O ₃Structure has and has Co ^{+ 3}Replace Cr ^{+ 3}Consistent lattice shrinks.The size of crystal is about half of observed size among the preparation embodiment 16.

Preparation embodiment 18

Prepare 90% chromium/10% Co catalysts (excessive NH of 6.7 equivalents ₄NO ₃400 ℃)

Except using the 96.05g NH that is dissolved in the 200mL water ₄(NO ₃) outside the solution-treated chromium/cobalt/cobalt oxide/hydroxide of (1.2 moles), the oxide preparation above repeating.

The conventional program of product analysis

Following conventional program explanation is used for the method for the product of fluorine analysis carbon reaction.The gas chromatograph (GC-MS) that use is furnished with mass selective detector is used for the organic product analysis in the part of line extraction whole reactor effluent.With long 20 feet (6.1m) * diameters 1/8 inch (0.32cm), contain and be positioned on the inertia carbon carrier The pipe of perfluorinated polyether (tubing) is realized gas chromatography. helium flow is that 30mL/min. gas-chromatography state is the initial 3 minutes time to keep 60 ℃, is warming up to 200 ℃ with 6 ℃/minute subsequently.

Before abandoning, handle the most of reactor effluent that contains organic product and inorganic acid such as HCl and HF with aqueous caustic.

All vapor reactions are all carried out under 1 atmospheric nominal pressure.

Explanation

The 12nd, CCl ₂F ₂The 13rd, CClF ₃

The 21st, CHCl ₂F 22 is CHClF ₂

The 23rd, CHF ₃The 32nd, CH ₂F ₂

The 112nd, CCl ₂FCCl ₂F 112a is CCl ₃CClF ₂

The 113rd, CCl ₂FCClF ₂113a is CCl ₃CF ₃

The 114th, CClF ₂CClF ₂114a is CF ₃CCl ₂F

The 115th, CF ₃CClF ₂The 116th, CF ₃CF ₃

The 122nd, CHCl ₂CClF ₂The 123rd, CHCl ₂CF ₃

123a is CHClFCClF ₂123b is CHF ₂CCl ₂F

The 124th, CHClFCF ₃124a is CHF ₂CClF ₂

The 125th, CHF ₂CF ₃132a is CHF ₂CHCl ₂

133a is CH ₂ClCF ₃The 134th, CHF ₂CHF ₂

134a is CH ₂FCF ₃143a is CH ₃CF ₃

152a is CH ₃CHF ₂The 1110th, CCl ₂=CCl ₂

The 1111st, CClF=CCl ₂1112a is CF ₂=CCl ₂

The 1113rd, CF ₂=CClF 1120 is CHCl=CCl ₂

The 1122nd, CHCl=CF ₂The 1130th, C ₂H ₂Cl ₂

The 1140th, CH ₂=CHCl 1141 is CHF=CH ₂

The 214th, C ₃Cl ₄F ₄214ab is CF ₃CCl ₂CCl ₂F

215aa is CF ₃CCl ₂CClF ₂215bb is CCl ₂FCClFCF ₃

216aa is CF ₃CCl ₂CF ₃216ba is CClF ₂CClFCF ₃

216ca is CClF ₂CF ₂CClF ₂216cb is CCl ₂FCF ₂CF ₃

217ba is CF ₃CClFCF ₃217ca is CClF ₂CF ₂CF ₃

The 218th, CF ₃CF ₂CF ₃224aa is CF ₃CCl ₂CHClF

224ba is CF ₃CClFCHCl ₂224caCClF ₂CF ₂CHCl ₂

225ba is CHClFCClFCF ₃225ca is CF ₃CF ₂CHCl ₂

225cb is CClF ₂CF ₂CHClF 225da is CF ₃CHClCClF ₂

226ca is CF ₃CF ₂CHClF 226da is CF ₃CHClCF ₃

227ca is CF ₃CF ₂CHF ₂227ea is CF ₃CHFCF ₃

235bb is CF ₃CClFCH ₂F 235da is CF ₃CHClCHF ₂

235fa is CF ₃CH ₂CClF ₂236fa is CF ₃CH ₂CF ₃

244eb is CF ₃CHFCH ₂Cl 245eb is CF ₃CHFCH ₂F

245fa is CF ₃CH ₂CHF ₂253fb is CF ₃CH ₂CH ₂Cl

254fb is CF ₃CH ₂CH ₂F 263fb is CF ₃CH ₂CH ₃

1213xa is CF ₃CCl=CCl ₂The 1214th, C ₃Cl ₂F ₄

The 1215th, C ₃ClF ₅1215xc is CF ₃CCl=CF ₂

The 1222nd, C ₃HCl ₃F ₂The 1223rd, C ₃HCl ₂F ₃

1223za is CCl ₂=CHCF ₃The 1224th, C ₃HClF ₄

1225zc is CF ₃CH=CF ₂1234yf is CH ₂=CFCF ₃

1234ze is E-and Z-CHF=CHCF ₃The 1316th, C ₄Cl ₂F ₆

The 1326th, C ₄HClF ₆HFP is CF ₂=CFCF ₃

TFE is CF ₂=CF ₂

Embodiment 19

Fluoridize CF ₃CHCl ₂

The chromium oxide that will replace (Cr/Co 95/5,29.04g, 20mL ,-12-+20 order, (1.68-0.84mm)) by the cobalt of preparation embodiment 15 described preparations be placed in heat in the sand bath of flowing, diameter is the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube. in (25cc/min, 4.2 * 10 of flowing of nitrogen ^-7m ³/ s) under, catalyst is heated to 175 ℃ from 77 ℃ with about 1.2 hours time. then, with 50cc/min (8.3 * 10 separately ^-7m ³/ s) flow is common HF and the nitrogen supplied with in reactor.1.5 after hour, nitrogen flow is reduced to 20cc/min (3.3 * 10 ^-7m ³/ s), the HF flow increases to 80cc/min (1.3 * 10 ^-6m ³/ s).Temperature of reactor is brought up to 413 ℃ gradually with 5 hours times, and remain on 413 ℃ following 0.6 hour.At the end of this period, stop HF stream, at 20sccm (3.3 * 10 ^-7m ³/ s) nitrogen flows down reactor is cooled to 300 ℃.

The catalyst for preparing above is placed in the reactor, cleans with nitrogen and HF down at 300 ℃. under 30 seconds time of contact, mol ratio is that HF and the HCFC-123 steam of 6:1 is fed in the reactor jointly.As follows by the reactor effluent that GC-MS analyzes.

Component Mole %

HFC-125 26.7

HCFC-124 49.2

HCFC-124a 0.2

CFC-114a 1.4

HCFC-123 22.1

Other product comprises CFC-113a, CFC-113, CFC-115.

Embodiment 20

Fluoridize CF ₃CHClF

The chromium oxide that will replace (Cr/Co 90/10,6.75g, 4mL, the 12-20 order, (1.68-0.84mm)) by the cobalt of preparation embodiment 16 described preparations be placed in heat in the kiln, diameter is the Inconel of 1/2 ＂ (1.27 centimetres) ^TMIn the nickel alloy reaction tube.(50cc/min, 8.3 * 10 of flowing at nitrogen ^-7m ³/ s) under, with about 25 minutes catalyst is heated to 400 ℃ from 200 ℃, make temperature be reduced to 300 ℃ then, keep nitrogen to flow simultaneously extra 80 minutes.Nitrogen flow is reduced to 35cc/min (5.8 * 10 ^-7m ³/ s), HF is with 12cc/min (2.0 * 10 then ^-7m ³/ s) flow enters in the reactor.After 35 minutes, temperature was increased to 325 ℃ after .60 minute, it is increased to 350 ℃.After 60 minutes, it is increased to 375 ℃.After 90 minutes, it is increased to 400 ℃.After 30 minutes, it is increased to 425 ℃.After 20 minutes, the flow of nitrogen is reduced to 15cc/min (2.5 * 10 ^-7m ³/ s), the flow of HF increases to 28cc/min (4.7 * 10 ^-7m ³/ s).After 20 minutes, the flow of nitrogen is reduced to 5cc/min (8.3 * 10 ^-8m ³/ s), the flow of HF increases to 36cc/min (6.0 * 10 ^-7m ³/ s).After 20 minutes, cut off the nitrogen flow, the flow of HF is increased to 40cc/min (6.7 * 10 ^-7m ³/ s), kept this state 120 minutes.Temperature of reactor is adjusted to 350 ℃, under 3.3 seconds time of contact, is that the HF of 2:1 and HCFC-124 steam supply are in reactor with mol ratio.As follows by the reactor effluent that GC-MS analyzes.

Component Mole %

HFC-125 19.1

CFC-115 48ppm

HCFC-124 77.5

HCFC-124a 0.4

HCFC-123 3.0

Embodiment 21

Fluoridize CF ₃CHClF

Will by preparation embodiment 18 described preparations, use excessive N H ₄NO ₃The chromium oxide that pretreated cobalt replaces (Cr/Co90/10,5.66g, 4mL, the 12-20 order, (1.68-0.84mm)) be placed in heat in the kiln, the diameter " Inconel of (1.27 centimetres) that is 1/2 ^TMIn the nickel alloy reaction tube.(50cc/min, 8.3 * 10 of flowing at nitrogen ^-7m ³/ s) under, with about 25 minutes catalyst is heated to 400 ℃ from 200 ℃, make temperature be reduced to 300 ℃ then, keep nitrogen to flow simultaneously extra 80 minutes.Nitrogen flow is reduced to 35cc/min (5.8 * 10 ^-7m ³/ s), HF is with 12cc/min (2.0 * 10 then ^-7m ³/ s) flow entered in the reactor after .35 minute, and temperature is increased to 325 ℃.After 60 minutes, it is increased to 350 ℃.After 60 minutes, it is increased to 375 ℃.After 90 minutes, it was increased to 400 ℃ after .30 minute, it was increased to 425 ℃ after .20 minute, the flow of nitrogen is reduced to 15cc/min (2.5 * 10 ^-7m ³/ s), the flow of HF increases to 28cc/min (4.7 * 10 ^-7m ³/ s).After 20 minutes, the flow of nitrogen is reduced to 5cc/min (8.3 * 10 ^-8m ³/ s), the flow of HF increases to 36cc/min (6.0 * 10 ^-7m ³/ s).After 20 minutes, cut off the nitrogen flow, the flow of HF is increased to 40cc/min (6.7 * 10 ^-7m ³/ s), keeping this state 120 minutes. temperature of reactor is adjusted to 350 ℃, under 3.3 seconds time of contact, is that the HF of 2:1 and HCFC-124 steam supply are in reactor with mol ratio.As follows by the reactor effluent that GC-MS analyzes.

Component Mole %

HFC-125 62.0

CFC-115 200ppm

HCFC-124 23.3

HCFC-124a 0.2

HCFC-133a 0.3

FCFC-114a 0.1

HCFC-123 14.0

FCFC-113 0.1

Embodiment 22

Fluoridize CCl ₂=CCl ₂

The chromium oxide that will replace (Cr/Co 90/10,32.26g, 20mL ,-12-+20 order, (1.68-0.84mm)) by the cobalt of preparation embodiment 16 described preparations be placed in heat in the sand bath of flowing, diameter is the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube. in (50cc/min, 8.3 * 10 of flowing of nitrogen ^-7m ³/ s) under, catalyst is heated to 246 ℃ from 50 ℃ with about 1.6 hours time.Under 175 ℃, with 20cc/min (3.3 * 10 ^-7m ³/ s) N ₂Clean one night of this catalyst, then, at 175 ℃ with 50cc/min (8.3 * 10 separately ^-7m ³/ s) flow is common HF and the N of supplying with in reactor ₂.1.3 hour after, nitrogen flow is reduced to 20cc/min (3.3 * 10 ^-7m ³/ s), the HF flow increases to 80cc/min (6.3 * 10 ^-6m ³/ s). temperature of reactor is increased to 375 ℃ gradually with 2 hours times, uses 10cc/min N down at 409 ℃ then ₂(1.7 * 10 ^-7m ³/ s) and 90cc/min (1.5 * 10 ^-6m ³/ s) HF handled extra 2.3 hours. at the end of this period, stop HF stream, at 20sccm (3.3 * 10 ^-7m ³/ s) nitrogen flows down reactor is cooled to 300 ℃.

The catalyst for preparing above is placed in the reactor, at 325 ℃ down with nitrogen and HF cleaning. temperature of reactor is adjusted to 375 ℃, under 15 seconds time of contact, is that the HF of 6:1 and tetrachloro-ethylene steam supply are in reactor with mol ratio.As follows by the reactor effluent that GC-MS analyzes.

Component Mole %

HFC-125 0.1

HCFC-124 1.9

HCFC-124a 0.3

CFC-114a 1.6

HCFC-123 8.6

HCFC-123a 1.4

HCFC-122 2.8

CFC-1112a 2.5

CFC-1111 9.8

HCC-1110 68.5

Other product comprises CFC-112, CFC-112a, CFC-113a, CFC-113, CFC-114a, HCFC-133a, HFC-23.

Embodiment 23

Fluoridize CF ₃CF ₂CHCl ₂And CClF ₂CF ₂The mixture of CHClF

The chromium oxide that will replace (Cr/Co 97/3,28.57g, 20mL ,-12-+20 order, (1.68-0.84mm)) by the cobalt of preparation embodiment 10 described preparations be placed in heat in the sand bath of flowing, diameter is the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube. under 150 ℃, with 25cc/min (4.2 * 10 ^-7m ³/ s) nitrogen cleaned this catalyst 16 hours. under 175 ℃, with N ₂Flow is increased to 50cc/min (8.3 * 10 ^-7m ³/ s) 0.5 hour. then, with 50cc/min (8.3 * 10 separately ^-7m ³/ s) flow is the common N that supplies with in reactor ₂And HF.1.2 after hour, nitrogen flow is reduced to 20cc/min (3.3 * 10 ^-7m ³/ s), the HF flow increases to 80cc/min (1.3 * 10 ^-6m ³/ s).Then, with 5.7 hours time temperature of reactor is brought up to 300 ℃ gradually.Close HF, with 20cc/min3.3 * 10 ^-7m ³/ s) about 16 hours of nitrogen cleaning reaction device.Then, make N ₂Be respectively 20cc/min (3.3 * 10 with the flow of HF ^-7m ³/ s) and 80cc/min (1.3 * 10 ^-6m ³/ s), and temperature of reactor is brought up to 410 ℃ from 298 ℃ with 3.5 hours, remain on then 410 ℃ following 2.3 hours. at the end of this period, stop HF stream, at 20sccm (3.3 * 10 ^-7m ³/ s) nitrogen flows down reactor is cooled to 300 ℃.

Temperature of reactor is adjusted to 325 ℃, under 30 seconds time of contact, be that the HF of 4:1 and the steam of HCFC-225cb/ca mixture (52.8GC area %225cb and 46.8GC area %225ca) are fed in the reactor jointly with mol ratio. as follows by the reactor effluent that GC-MS analyzes.

Component GC area %

HCFC-225ca 7.5

HCFC-225cb 16.7

HCFC-224ca 4.0

HCFC-226ca 22.6

HCFC-226cb 30.2

HFC-227ca 14.8

Other product comprises CFC-217ca, HCFC-226ba, HCFC-226da, HCFC-1224, CFC-216, HCFC-225 isomers, CFC-215ca, HCFC-1223.

Embodiment 24

Fluoridize CF ₃CCl=CCl ₂

The chromium oxide that will replace (Cr/Co 98/2,28.04g, 20mL ,-12-+20 order, (1.68-0.84mm)) by the cobalt of preparation embodiment 5 described preparations be placed in heat in the sand bath of flowing, diameter is the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube.(50cc/min, 8.3 * 10 of flowing at nitrogen ^-7m ³/ s) under, catalyst is heated to 177 ℃ from 90 ℃ with about 0.7 hour time. then, with 50cc/min (8.3 * 10 separately ^-7m ³/ s) flow is common HF and the N of supplying with in reactor ₂.2 hour after, nitrogen flow is reduced to 20cc/min (3.3 * 10 ^-7m ³/ s), the HF flow increases to 80cc/min (1.3 * 10 ^-6m ³/ s). then, temperature of reactor is brought up to 298 ℃ gradually with 3.5 hours times.Close HF, under 299 ℃, with 20cc/min (3.3 * 10 ^-7m ³/ s) N ₂One night of cleaning reaction device.Second day, make N ₂Be respectively 20cc/min (1.3 * 10 with the HF flow ^-7m ³/ s) and 80cc/min (1.3 * 10 ^-6m ³/ s), and temperature of reactor is increased to 400 ℃ with 1.7 hours. make temperature of reactor remain on 400-410 ℃ extra 1.3 hours down.At the end of this period, stop HF stream, at 20sccm (3.3 * 10 ^-7m ³/ s) nitrogen flows down reactor is cooled to 300 ℃. and under 15 seconds time of contact, to be the HF of 20:1 and HCFC-1213xa be fed in the reactor with the form of steam mol ratio jointly.It is under 300 ℃ the temperature of reactor, as follows by the reactor effluent that GC-MS analyzes.

Component GC area %

HCFC-226da 90.0

CFC-216ba 0.2

CFC-216aa 4.3

CFC-217ba 1.0

CFC-1215 1.1

Other product comprises HFC-1225, CFC-217ca, CFC-114, CFC-114a, CFC-113, CFC-215, HCFC-225da.

Embodiment 25

Fluoridize CF ₃CCl=CCl ₂

Will by the cobalt/chromated oxide of preparation embodiment 6 described preparations (Cr/Co98/2 is 550 ℃ of following calcination, 32.0g, 20mL ,-12-+20 order, (1.68-0.84mm)) be placed in heat in the sand bath of flowing, diameter is the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube.(50cc/min, 8.3 * 10 of flowing at nitrogen ^-7m ³/ s) under, catalyst is heated to 176 ℃ from 65 ℃ with about 0.8 hour time. then, with 50cc/min (8.3 * 10 separately ^-7m ³/ s) flow is common HF and the N of supplying with in reactor ₂0.6 after hour, with N ₂Be adjusted to 20cc/min (3.3 * 10 respectively with the HF flow ^-7m ³/ s) and 80cc/min (1.3 * 10 ^-6m ³/ s), with 3 hours temperature of reactor is increased to 411 ℃ simultaneously.Catalyst was remained on 411 times 0.75 hour, then, with N ₂Be adjusted to 10cc/min (1.7 * 10 respectively with the HF flow ^-7m ³/ s) and 50cc/min (8.3 * 10 ^-7m ³/ s), make temperature of reactor remain on 411 ℃ simultaneously and descended extra 2 hours.At the end of this period, stop HF stream, at 15sccm (2.5 * 10 ^-7m ³/ s) nitrogen flows down reactor is cooled to 295 ℃.Under 15 seconds time of contact, be that hydrogen fluoride and the CFC-1213xa of 20:1 is fed in the reactor jointly with mol ratio.As follows by the reactor effluent that GC-MS analyzes.

GC area %

Component 300 ℃

HCFC-226da 25.4

CFC-216aa 20.8

CFC-1215 35.7

CFC-1214′s 10.0

CFC-217ba 0.9

CFC-215aa 1.5

CFC-215bb 1.7

CFC-1213xa 2.4

Other product comprises HFP, CFC-216ba, CFC-216cb, CFC-114, CFC-114a, CFC-113, CFC-112.

Comparative Examples 26

Fluoridize CF ₃CCl=CCl ₂

Granulation, the commercial cobalt chromite sample (CoCr of screening ₂O ₄, CAS Reg.No.[12016-69-2], 40.8g, 20mL ,-12-+20 order, (1.68-0.84mm)), and to be placed in the diameter that heats in the sand bath of flowing be the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube.(50cc/min, 8.3 * 10 of flowing at nitrogen ^-7m ³/ s) under, catalyst is heated to 174 ℃ from 80 ℃ with about 1.5 hours time. then, with 50cc/min (8.3 * 10 separately ^-7M/s) flow is common HF and the N of supplying with in reactor ₂0.2 after hour, nitrogen flow is adjusted to 20cc/min (3.3 * 10 ^-7m ³/ s), the HF flow increases to 80cc/min (1.3 * 10 ^-6m ³/ s). then, catalyst is heated to 401 ℃ from 175 ℃ with 3.2 hours times.Stop HF stream then, at 20sccm (3.3 * 10 ^-7m ³/ s) nitrogen flows down reactor is cooled to 300 ℃.With mol ratio is that hydrogen fluoride and the CFC-1213xa of 20:1 is fed in the reactor 15 seconds times of contact jointly.As follows by the reactor effluent that GC-MS analyzes.

GC area %

Component 300 ℃

CFC-1213xa 97.9

CFC-112 0.5

CFC-215aa 0.2

CFC-1214′s 0.5

CFC-1215 0.9

Embodiment 27

Chlorofluorination ethene

The catalyst that uses in this experiment is the catalyst that uses among the embodiment 24.Temperature of reactor is adjusted to 250 ℃, under 15 seconds time of contact, is that the steam of HF, ethene and the chlorine of 12:1:1 is fed in the reactor jointly with mol ratio.Under 250 ℃, the GC-MS of reactor effluent analyzes and shows below.

Component GC area %

Ethene 6.1

HFC-1141 11.4

HFC-152a 47.3

HCC-1140 33.4

Other product comprises HFC-143a, COF ₂, HCFC-142, HCC-1130, HCC-150.

Embodiment 28

Chlorofluorination ethane

Use cobalt to replace chromium oxide in this experiment from embodiment 27.Temperature of reactor is adjusted to 350 ℃, under 15 seconds time of contact, is that HF, the CFC-1213xa of 10:1:4 and the steam of chlorine are fed in the reactor jointly with mol ratio.Under 350 ℃ the temperature of reactor, as follows by the reactor effluent that GC-MS analyzes.

Component GC area %

HCFC-133a 37.0

HFC-143a 2.1

HFC-134 1.6

HCC-1120 22.9

HCC-1130(two) 19.7

HCC-1140 1.3

HCC-1110 7.2

CFC-1111 1.2

Other product comprises HFC-1141, CFC-115, CFC-114a, HCFC-123a, HCFC-132a.

Embodiment 29

Chlorofluorination CF ₃CCl=CCl ₂

The chromium oxide that will replace (Cr/Co 99/1,29.0g, 20mL ,-12-+20 order, (1.68-0.84mm)) by the cobalt of preparation embodiment 2 described preparations be placed in heat in the sand bath of flowing, diameter is the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube. in (50cc/min, 8.3 * 10 of flowing of nitrogen ^-7m ³/ s) under, catalyst is heated to 174 ℃ from 52 ℃ with about 1 hour time. then, with 50cc/min (8.3 * 10 separately ^-7m ³/ s) flow is common HF and the N of supplying with in reactor ₂2 hours; During this time, significant heat release is arranged.Then, nitrogen flow is reduced to 20cc/min (3.3 * 10 ^-7m ³/ s), the HF flow increases to 80cc/min (1.3 * 10 ^-6m ³/ s).With 3 hours temperature of reactor is brought up to 407 ℃ gradually, and remain on 406 ℃ following 1.3 hours. then, stop HF stream, flow down at 20sccm nitrogen reactor be cooled to 300 ℃. at 300 ℃ down with being fed to the chlorofluorination that HF, CFC-1213xa in the reactor and chlorine begin CFC-1213xa jointly, under .320 ℃ of 15 seconds time of contact, mol ratio is that mol ratio is that the GC-MS of the reactor effluent of 30:1:2 is analyzed as follows under 20:1:4 (respectively for HF, CFC-1213xa and chlorine) and 400 ℃.

GC area %

Component 300 ℃ 450 ℃

HCFC-226da 1.4 0.03

CFC-216ba 21.1 8.9

CFC-216aa 21.9 40.8

CFC-217ba 16.8 47.4

CFC-215aa 35.9 0.1

CFC-217ca 0.7 2.0

CFC-216cb 1.0 -

Other product comprises CFC-1215, CFC-114, CFC-114a, HCFC-225da, CFC-113.

Embodiment 30

Chlorofluorination CF ₃CCl=CCl ₂

Will by the cobalt/chromated oxide of preparation embodiment 13 described preparations (Cr/Co95/5,21.8g, 15mL ,-12-+20 order, (1.68-0.84mm)) be placed in heat in the sand bath of flowing, diameter is the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube.(50cc/min, 8.3 *-10 of flowing at nitrogen ^-7m ³/ s) under, catalyst is heated to 173 ℃ from 52 ℃ with about 1 hour time. then, to be respectively 2cc/min (4.2 * 10 ^-7m ³/ s) and 75cc/min (1.25 * 10 ^-6m ³/ s) flow is common in reactor supplies with HF and after nitrogen .2.2 hour, separately with nitrogen and HF Flow-rate adjustment to 50cc/min (8.3 * 10 ^-7m ³/ s), and temperature of reactor is increased to 299 ℃ gradually with 3 hours. under 299 ℃, with 20cc/min (3.3 * 10 ^-7m ³/ s) one night of nitrogen cleaning reaction device.Then, to be respectively 80cc/min (1.3 * 10 ^-6m ³/ s) and 20cc/min (3.3 * 10 ^-7m ³/ s) flow is common in reactor supplied with HF and nitrogen 0.6 hour.Then, with 2 hours temperature of reactor is brought up to 400 ℃.The nitrogen flow is reduced to 10cc/min (1.7 * 10 ^-7m ³/ s), and temperature is increased to 410 ℃.After 1 hour, with adjustment to 280 ℃. under 15 seconds time of contact, under 280 ℃, with the chlorofluorination that is fed in the reactor jointly, HF, CFC-1213xa that mol ratio is 20:1:4 and chlorine begin CFC-1213xa.The GC-MS of 320 ℃ and 350 ℃ following reactor effluents is analyzed as follows.

GC area %

Component 320 ℃ 450 ℃

HCFC-226da 1.2 0.4

CFC-216ba 23.2 26.6

CFC-216aa 19.5 35.3

CFC-217ba 8.7 9.8

CFC-215aa 44.5 25.8

Other product comprises CFC-217ca, CFC-1215, CFC-115, CFC-13, CFC-114, CFC-114a, CFC-216cb, CFC-113, CFC-214, CFC-215.

Embodiment 31

Chlorofluorination CF ₃CCl=CCl ₂

Will by preparation embodiment 15 described preparations, with the pretreated cobalt/chromated oxide (Cr/Co95/5 of excessive ammonium nitrate, 21.8g, 15mL ,-12-+20 order, (1.68-0.84mm)) be placed in heat in the sand bath of flowing, diameter is the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube.(25cc/min, 4.2 * 10 of flowing at nitrogen ^-7m ³/ s) under, catalyst is heated to 200 ℃ from 77 ℃ with about 1.3 hours time, and remained under this temperature about 63 hours. then, under 177 ℃, with 50cc/min (8.3 * 10 separately ^-7m ³/ s) flow is common HF and the nitrogen supplied with in reactor.1.6 after hour, HF and nitrogen flow are adjusted to 80cc/min (1.3 * 10 respectively ^-6m ³/ s) and 20cc/min (3.3 * 10 ^-7m ³/ s), and temperature of reactor is increased to 413 ℃ with 5 hours. remain on 413 ℃ after following 0.7 hour, stop the HF flow, under 300 ℃, clean one night of this reactor with nitrogen.Under 15 seconds time of contact, under 300 ℃, the chlorofluorination that HF, CFC-1213xa that usefulness is fed in the reactor jointly, mol ratio is 20:1:4 and chlorine begin CFC-1213xa.Under 320 ℃, molar feed ratio is 20:1:4, and under 350 ℃, molar feed ratio is that the GC-MS of reactor effluent under the 30:1:2 is analyzed as follows.

GC area %

320℃ 350℃ 350℃

Component 20:1:4 20:1:4 30:1:2

HCFC-226da 1.8 0.9 3.0

CFC-216ba 17.6 18.6 12.2

CFC-216aa 22.5 34.1 42.9

CFC-217ba 18.1 20.4 27.6

CFC-215aa 36.7 23.8 12.0

Other product comprises CFC-217ca, CFC-1215, CFC-115, CFC-114, CFC-114a, CFC-216cb, CFC-113, CFC-214, CFC-215.

Embodiment 32

Chlorofluorination CF ₃CCl=CCl ₂

Will by the cobalt/chromated oxide of preparation embodiment 11 described preparations (Cr/Co 97/3,31.6g, 20mL ,-12-+20 order, (1.68-0.84mm)) be placed in heat in the sand bath of flowing, diameter is the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube.(50cc/min, 8.3 * 10 of flowing at nitrogen ^-7m ³/ s) under, catalyst is heated to 174 ℃ from 47 ℃ with about 0.8 hour time. then, with 50cc/min (8.3 * 10 separately ^-7m ³/ s) flow is common HF and the nitrogen supplied with in reactor.0.7 after hour, respectively with nitrogen and HF Flow-rate adjustment to 20cc/min (3.3 * 10 ^-7m ³/ s) and 80cc/min (1.3 * 10 ^-6m ³/ s).After keeping 1.7 hours under 175 ℃, temperature of reactor is brought up to 410 ℃ gradually with 3.4 hours.After 1 hour, make temperature drop to 298 ℃ from 410 ℃, cut off the HF flow, clean one night of this reactor with nitrogen.Under 15 seconds time of contact, under 300 ℃, the chlorofluorination that HF, CFC-1213xa that usefulness is fed in the reactor jointly, mol ratio is 20:1:4 and chlorine vapor begin CFC-1213xa.Under 320 ℃ and 350 ℃, molar feed ratio is 20:1:4, and under 400 ℃, molar feed ratio is that the GC-MS of reactor effluent under the 30:1:2 is analyzed as follows.

GC area %

Component 320 ℃ 350 ℃ 400 ℃

HCFC-226da 3.0 1.8 1.1

CFC-216ba 17.1 24.7 19.6

CFC-216aa 14.6 19.6 33.7

CFC-217ba 14.9 21.0 31.7

CFC-215aa 44.1 29.6 10.6

CFC-215bb 3.7 0.03 -

Embodiment 33

Chlorofluorination CF ₃CCl=CCl ₂

Will by the cobalt/chromated oxide of preparation embodiment 10 described preparations (Cr/Co 97/3,28.2g, 20mL ,-12-+20 order, (1.68-0.84mm)) be placed in heat in the sand bath of flowing, diameter is the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube. under 150 ℃, with 25cc/min (8.3 * 10 ^-7m ³/ s) nitrogen cleaned this catalyst 16 hours.Under 175 ℃, the N2 flow is increased to 50cc/min (8.3 * 10 ^-7M/s) 0.5 hour.Then, with 50cc/min (8.3 * 10 separately ^-7m ³/ s) flow is the common N that supplies with in reactor ₂And HF.1.2 after hour, nitrogen flow is reduced to 20cc/min (3.3 * 10 ^-7m ³/ s), the HF flow increases to 80cc/min. then, temperature of reactor is brought up to 300 ℃ gradually with 5.7 hours times.Close HF, under 300 ℃, with 20cc/min (3.3 * 10 ^-7m ³/ s) about 16 hours of nitrogen cleaning reaction device.Then, make N ₂Be respectively 20cc/min (3.3 * 10 with the flow of HF ^-7m ³/ s) and 80cc/min (1.3 * 10 ^-6m ³/ s), and temperature of reactor is brought up to 410 ℃ from 298 ℃ with 3.5 hours, remain on then 410 ℃ following 2.3 hours.At the end of this period, stop HF stream, flow down at 20sccm nitrogen reactor is cooled to 300 ℃.Under 15 seconds time of contact, under 300 ℃, be fed in the reactor jointly, HF, CFC-1213xa that mol ratio is 20:1:4 and chlorine vapor begin CFC-1213xa, and chlorofluorination .320 ℃ and the GC-MS of 350 ℃ of following reactor effluents are analyzed as follows.

GC area %

Component 320 ℃ 350 ℃

HCFC-226da 2.0 1.0

CFC-216ba 16.8 21.2

CFC-216aa 26.4 32.5

CFC-217ba 14.2 19.7

CFC-215aa 36.423.1

Other product comprises CFC-217ca, CFC-1215, HFC-1225, CFC-115, CFC-13, CFC-114, CFC-114a, CFC-216cb, CFC-113.

Embodiment 34

Chlorofluorination CF ₃CCl=CCl ₂

Will by the cobalt/chromated oxide of preparation embodiment 3 described preparations (Cr/Co98/2 is 400 ℃ of following calcination, 21.068,15mL ,-12-+20 order, (1.38-0.84mm)) be placed in heat in the sand bath of flowing, diameter is the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube.(77cc/min, 8.3 * 10 of flowing at nitrogen ^-7m ³/ s) under, catalyst is heated to 176 ℃ from 77 ℃ with about 1.7 hours time. then, with 50cc/min (8.3 * 10 separately ^-7m ³/ s) flow is common HF and the N of supplying with in reactor ₂After 1 hour, temperature of reactor is increased to 326 ℃, simultaneously with HF and N with 3 hours ₂Flow remains 50cc/min (8.3 * 10 ^-7m ³/ s). and then, with N ₂Be adjusted to 25cc/min (4.2 * 10 respectively then with the HF flow ^-7m ^-3/ s) and 50cc/min (8.3 * 10 ^-7m ^-3/ s), with 1 hour temperature of reactor is increased to 401 ℃ simultaneously.Then, with N ₂Be adjusted to 10cc/min and 50cc/min (8.3 * 10 respectively then with the HF flow ^-7m ^-3/ s), make simultaneously temperature of reactor remain on 401 ℃ following 1 hour.At the end of this period, stop HF stream, flow down at 20sccm nitrogen reactor is cooled to 280 ℃.Under 15 seconds time of contact, under 280 ℃, be fed in the reactor jointly, (molar feed ratio is 30:1:2 for chlorofluorination .320 ℃ (20:1:4) that HF, CFC-1213xa that mol ratio is 20:1:4 and chlorine vapor begin CFC-1213xa and 400 ℃; Time of contact=15 second) the GC-MS data of reactor effluent are as follows down.

GC area %

Component 320 ℃ 400 ℃

HCFC-226da 1.7 0.02

CFC-216ba 23.1 4.9

CFC-216aa 19.0 46.4

CFC-216cb 0.4 -

CFC-217ba 15.3 46.6

CFC-215aa 38.3 0.03

CFC-215bb 0.1 -

CFC-214ab - -

Other product comprises CFC-217ca, CFC-1215, CFC-115, CFC-114, CFC-114a, CFC-113, CFC-1213xa, CFC-112.

Embodiment 35

Chlorofluorination CF ₃CCl=CCl ₂

Will by the cobalt/chromated oxide of preparation embodiment 4 described preparations (Cr/Co 98/2,900 ℃ of following calcination, 27.52g, 15mL ,-12-+20 order, (1.68-0.84mm)) be placed in heat in the sand bath of flowing, diameter is the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube. in (50cc/min, 8.3 * 10 of flowing of nitrogen ^-7m ³/ s) under, catalyst is heated to 174 ℃ from 96 ℃ with about 0.5 hour time.Then, with 50cc/min (8.3 * 10 separately ^-7m ³/ s) flow is common HF and the N of supplying with in reactor ₂After keeping 0.3 hour under 175 ℃, respectively with HF and N ₂Flow-rate adjustment to 80cc/min (1.3 * 10 ^-6m ³/ s) and 20cc/min (3.3 * 10 ^-7m ³/ s), then, temperature is increased to 400 ℃ with 5 hours. at the end of this period, stop HF stream, at 20sccm (3.3 * 10 ^-7m ³/ s) nitrogen flows down reactor is cooled to 300 ℃.Under 15 seconds time of contact, under 300 ℃, the chlorofluorination that HF, CFC-1213xa that usefulness is fed in the reactor jointly, mol ratio is 20:1:4 and chlorine vapor begin CFC-1213xa.The GC-MS of 320 ℃ and 400 ℃ following reactor effluents is analyzed as follows.

GC area %

Component 320 ℃ 400 ℃

HCFC-226da 0.4 0.1

CFC-216ba 9.2 34.9

CFC-216aa 19.6 26.6

CFC-216cb 2.0 2.4

CFC-217ba 10.4 14.8

CFC-215aa 23.9 17.5

CFC-215bb 28.6 1.6

CFC-214ab 3.4 0.04

Embodiment 36

Chlorofluorination CF ₃CCl=CCl ₂

Hydrogen fluoride, CFC-1213xa and chlorine are fed in the reactor that contains catalyst among the embodiment 25 jointly, 15 seconds times of contact .320 ℃ of (air inlet HF:1213xa:Cl ₂Mol ratio is 20:1:4) and 375 ℃ of (air inlet HF:1213xa:Cl ₂Mol ratio is 30:1:2) descend the GC-MS of reactor effluent to be analyzed as follows.

GC area %

Component 320 ℃ 375 ℃

CFC-217ba 11.0 22.1

CFC-216aa 22.4 27.5

CFC-216ba 15.5 33.8

CFC-216cb 2.3 3.1

HCFC-226da 0.7 0.5

CFC-215aa 27.6 9.6

CFC-215bb 18.9 1.5

CFC-1213xa - -

Other product comprises CFC-115, CFC-217ca, CFC-1215, CFC-114, CFC-114a, CFC-1214 ' s, CFC-113, CFC-112, CFC-214ab.

Embodiment 37

Chlorofluorination CF ₃CCl=CCl ₂

Will by the cobalt/chromated oxide of preparation embodiment 9 described preparations (Cr/Co98/2 is 550 ℃ of following calcination, 29.4g, 20mL ,-12-+20 order, (1.68-0.84mm)) be placed in heat in the sand bath of flowing, the diameter " Inconel of (1.58 centimetres) that is 5/8 ^TMIn the nickel alloy reaction tube.Use nitrogen (50cc/min, 8.3 * 10 down at 174 ℃ ^-7m ³/ s) about 72 hours of cleaning catalyst.Then, with 50cc/min (8.3 * 10 separately ^-7m ³/ s) flow is common HF and the N of supplying with in reactor ₂After keeping 0.8 hour under 175 ℃, respectively with HF and N ₂Flow-rate adjustment to 80cc/min (1.3 * 10 ^-6m ³/ s) and 20cc/min (3.3 * 10 ^-7m ³/ s), then, temperature is increased to 400 ℃ with 4.3 hours.Respectively with HF and N ₂Flow-rate adjustment to 50cc/min (8.3 * 10 ^-7m ^-3/ s) and 10cc/min (1.7 * 10 ^-7m ^-3/ s), make reactor remain on 406 ℃ simultaneously and descended extra 1.7 hours. at the end of this period, stop HF stream, at 20sccm (3.3 * 10 ^-7m ³/ s) nitrogen flows down reactor is cooled to 300 ℃. under 15 seconds time of contact, under 300 ℃, chlorofluorination .300 ℃ of (the air inlet HF:1213xa:Cl that HF, CFC-1213xa that usefulness is fed in the reactor jointly, mol ratio is 20:1:4 and chlorine vapor begin CFC-1213xa ₂Mol ratio is 20:1:4) and 400 ℃ of (air inlet HF:1213xa:Cl ₂Mol ratio is 30:1:2) descend the GC-MS of reactor effluent to be analyzed as follows.

GC area %

Component 300 ℃ 400 ℃

CFC-217ba 11.1 36.7

CFC-216aa 18.7 36.6

CFC-216ba 18.4 21.7

CFC-216cb 1.6 -

HCFC-226da 1.3 0.2

CFC-215aa 44.8 2.6

CFC-215bb 2.6 -

CFC-1213xa - -

Other product comprises FC-218, CFC-13, CFC-115, CFC-217ca, CFC-1215, CFC-114, CFC-114a, CFC-1214 ' s, CFC-113, CFC-214ab.

Comparative Examples 38

Chlorofluorination CF ₃CCl=CCl ₂

Hydrogen fluoride, CFC-1213xa and chlorine are fed in the reactor that contains from cobalt chromite catalyst Comparative Examples 26, that HF handled jointly; 15 seconds times of contact.375 ℃ of (air inlet HF:1213xa:Cl ₂Mol ratio is 20:1:4) descend the GC-MS of reactor effluent to be analyzed as follows.

GC area %

Component 375 ℃

CFC-217ba 0.2

CFC-216aa 0.6

CFC-216ba 0.4

CFC-216cb 3.1

CFC-215aa 10.5

CFC-215bb 24.9

CFC-214ab 27.4

CFC-1215 1.0

CFC-1214′s 12.5

CFC-1213xa 21.6

Other product comprises CFC-115, CFC-216cb, CFC-114, CFC-114a, CFC-1214 ' s, CFC-112, CFC-214ab.

Comparative Examples 39

Chlorofluorination CF ₃CCl=CCl ₂

Will by 100% chromium oxide (III) of comparative preparation embodiment 1 described preparation (400 ℃ of following calcination, 27.8g, 20mL ,-12-+20 order, (1.68-0.84mm)) be placed in heat in the sand bath of flowing, diameter is the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube.(50cc/min, 8.3 * 10 of flowing at nitrogen ^-7m ³/ s) under, catalyst is heated to 200 ℃ from 77 ℃ with about 1 hour time.Then, use nitrogen (20cc/min, 3.3 * 10 down at 174 ℃ ^-7m ³/ s) one night of cleaning catalyst. then, under 175 ℃, with 50cc/min (8.3 * 10 separately ^-7m ³/ s) flow is common in reactor to be supplied with HF and after nitrogen .1 hour, HF and nitrogen flow is adjusted to 80cc/min (1.3 * 10 respectively ^-6m ³/ s) and 20cc/min (3.3 * 10 ^-7m ³/ s), and temperature of reactor is increased to 410 ℃ with 3.6 hours. stop the HF flow, under 300 ℃, clean one night of this reactor with nitrogen.Under 15 seconds time of contact, under 300 ℃, the chlorofluorination that HF, CFC-1213xa that usefulness is fed in the reactor jointly, mol ratio is 20:1:4 and chlorine vapor begin CFC-1213xa.300 ℃ and 400 ℃ (molar feed ratio is 30:1:2) GC-MS of reactor effluent down are analyzed as follows.

GC area %

Component 300 ℃ 400 ℃

HCFC-226da 2.4 0.03

CFC-216ba 21.6 6.4

CFC-216aa 19.8 67.4

CFC-217ba 11.1 24.1

CFC-217ca 0.4 1.2

CFC-215aa 42.9 0.2

Other product comprises FC-218, CFC-1215, CFC-115, CFC-114, CFC-114a, CFC-216cb, CFC-113, CFC-112.

Embodiment 40

Isomerization 1:1CF ₃CClFCClF ₂/ CF ₃CCl ₂CF ₃Mixture

The catalyst that uses among the embodiment 34 is turned back in the reactor, and use nitrogen to clean up to 350 ℃.Then, be that mixture and the nitrogen of the CFC-216ba/216aa (50.2GC area %216ba and 49.8GC area %216aa) of 1:4 is fed in the reactor 30 seconds times of contact jointly with mol ratio.The GC-MS of reactor effluent is analyzed as follows.

Component GC area %

CFC-216ba 0.75

CFC-216aa 84.0

CFC-217ba 7.6

CFC-215aa 1.0

CFC-1213xa 3.9

CFC-1215 0.60

Other product comprises CFC-115, FC-218, CFC-217ca, CFC-114, CFC-114a, CFC-216cb, HCFC-226da, HCFC-225da, CFC-1214, CFC-215bb.

Embodiment 41

Fluoridize CF ₃CHClF/CClF ₂CHF ₂Mixture

The chromium oxide that will replace (Cr/Co95/5,29.04g, 20mL ,-12-+20 order, (1.68-0.84mm)) by the cobalt of preparation embodiment 15 described preparations be placed in heat in the sand bath of flowing, diameter is the Inconel of 5/8 ＂ (1.58 centimetres) ^TMIn the nickel alloy reaction tube.(25cc/min, 3.3 * 10 of flowing at nitrogen ^-7m ³/ s) under, catalyst is heated to 175 ℃ from 77 ℃ with about 1.2 hours time.Then, with 50cc/min (8.3 * 10 separately ^-7m ³/ s) flow is common in reactor to be supplied with HF and after nitrogen .1.5 hour, nitrogen flow is reduced to 20cc/min (3.3 * 10 ^-7m ³/ s), the HF flow increases to 80cc/min (1.3 * 10 ^-6m ³/ s).Temperature of reactor is brought up to 413 ℃ gradually with 5 hours times, and remain on 413 ℃ extra 0.6 hour down. at the end of this period, stop HF stream, flow down at 20sccm nitrogen reactor is cooled to 300 ℃.Under 10 seconds time of contact, be that the HF of 4:1 and the mixture of HCFC-124 and HCFC-124a steam (52.1GC area %124a and 44.2GC area %124) are fed in the reactor jointly with mol ratio.The GC-MS of 300 ℃ of following reactor effluents is analyzed as follows.

Component Mole %

HFC-125 44.1

HCFC-124 24.7

HCFC-124a 25.0

CFC-133a 0.9

HCFC-123 2.7

Other product comprises the impurity in the parent material: HFC-32, HFC-143a, HFC-134a, HFC-134 and byproduct: HFC-23, CFC-115, CFC-114a, HCFC-123a, HCFC-123b, CFC-113.

Embodiment 42

Disproportionation CF ₃CHClF/CClF ₂CHF ₂Mixture

The mixture of nitrogen and HCFC-124 and HCFC-124a (52.1GC area %124a and 44.2GC area%124) is fed in the reactor that contains the catalyst that uses among the embodiment 41 jointly.The mol ratio of nitrogen and 124/124a mixture is 4:1, and be 10 seconds time of contact.The GC-MS of 250 ℃ and 300 ℃ following reactor effluents is analyzed as follows.

GC mole %

Component 250 ℃ 300 ℃

HFC-125 24.6 55.2

HCFC-124 19.9 12.1

HCFC-124a 37.7 1.7

CFC-133a 1.6 2.1

HCFC-123 13.9 18.1

HCFC-123a 0.3 0

HCC-1110 - 4.7

HCC-1120 0.8 1.7

CFC-1111 0.2 2.5

Other product comprises HFC-23, HFC-32, HFC-143a, CFC-115, CFC-114a, HCFC-123b, CFC-113, HCFC-122.

Embodiment 43

CClF ₂CCl ₂F/CF ₃CCl ₃The isomerization of mixture and disproportionation

The mixture of nitrogen and CFC-113 and CFC-113a (52.9GC mole %113a and 47.1GCmole%113) is fed in the reactor that contains the catalyst that uses among the embodiment 42 jointly. the mol ratio of nitrogen and 113/113a mixture is 4:1, and be 15 seconds time of contact.The GC-MS of 150 ℃ and 300 ℃ following reactor effluents is analyzed as follows.

Mole %

Component 150 ℃ 300 ℃

CFC-115 - 1.7

CFC-114 - 6.2

CFC-114a 21.2 24.5

CFC-1112a 10.4 8.5

CFC-113 27.2 10.4

CFC-113a 30.0 33.3

CFC-112/112a 10.7 9.8

HCC-1110 0.03 4.7

Other product comprises CFC-13, HCFC-1122, CFC-1113, CFC-1111, CFC-1316.

Embodiment 44

Disproportionation CF ₃CCl ₂F

With mol ratio is that the nitrogen of 4:1 and CFC-114a (99.95GC mole %114a) are fed in the reactor that contains the catalyst that uses among the embodiment 43 15 seconds times of contact jointly.The GC-MS of 250 ℃ and 350 ℃ following reactor effluents is analyzed as follows.

Mole %

Component 250 ℃ 350 ℃

CFC-115 18.5 38.1

CFC-114 - 2.3

CFC-114a 64.6 30.6

CFC-1112a 0.2 0.7

CFC-113 0.03 0.7

CFC-113a 15.8 24.6

CFC-112/112a - 0.2

HCC-1110 0.04 1.8

Other product comprises CFC-13, FC-116, HCFC-1122, CFC-1113, HCFC-123, CFC-1111, CFC-1316.

Embodiment 45

CClF ₂CClF ₂/ CF ₃CClF ₂The disproportionation of mixture and isomerization

The mixture of nitrogen and CFC-114 and CFC-114a (87.3GC mole %114 and 12.6GC mole %114a) is fed in the reactor that contains the catalyst that uses among the embodiment 44 jointly.The mol ratio of nitrogen and 114/114a mixture is 4:1, and be 15 seconds time of contact.The GC-MS of 300 ℃ and 350 ℃ following reactor effluents is analyzed as follows.

Mole %

Component 300 ℃ 350 ℃

CFC-115 13.6 30.5

CFC-114 65.9 34.0

CFC-114a 11.0 18.1

CFC-1112a 1.4 1.9

CFC-113 4.8 4.4

CFC-113a 2.0 6.6

CFC-112/112a 0.2 0.4

HCC-1110 0.4 3.0

Other product comprises HFC-23, CFC-13, FC-116, HCFC-1122, CFC-1113, CFC-1111.

Embodiment 46

CF ₃CH ₂CF ₃Dehydrofluorination

Nitrogen and HFC-236fa are fed in the reactor that contains the catalyst that uses among the embodiment 45 jointly.The mol ratio of nitrogen and 236fa is 4:1, and be 15 seconds time of contact.The GC-MS of 300 ℃ and 350 ℃ following reactor effluents is analyzed as follows.

Mole %

Component 300 ℃ 350 ℃

HFC-236fa 91.0 81.5

HFC-1225zc 7.21 7.1

Other product comprises HFC-143a, CFC-1215, HCFC-226da, HCFC-1224, HCFC-1326, HCFC-1223, CFC-216aa, CFC-217ba.

Embodiment 47

CH ₃CHF ₂Dehydrofluorination

Nitrogen and HFC-152a are fed in the reactor that contains the catalyst that uses among the embodiment 45 jointly.The mol ratio of nitrogen and 152a is 4:1, and be that the GC-MS of 15 seconds .250 ℃ and 350 ℃ following reactor effluents is analyzed as follows time of contact.

Mole %

Component 250 ℃ 350 ℃

HFC-152a 63.1 16.7

HFC-1141 36.4 82.0

Other product comprises HCFC-151a, HCC-1140, ethene, methane.

Embodiment 48

Isomerization hexafluoro cyclopropane

With the catalyst that uses among the embodiment 34 (15mL 21.35g) turns back in the reactor, and under 350 ℃, uses nitrogen, cleans with HCl subsequently. then, be that nitrogen and the hexafluoro cyclopropane of 2:1 is fed in the reactor jointly with mol ratio; Time of contact, the GC-MS of 30 seconds .150 ℃ of following reactor effluents was analyzed as follows.

The GC area%

Component 150 ℃

HFP 98.0

TFE 1.1

HFC-23 0.4

HFC-227ea 0.2

Other product comprises HFC-125, CFC-217ba, FC-1318my, PFIB, CFC-1215 ' s.

Embodiment 49

The chlorination defluorinateization of fluoroform

With the catalyst that uses among the embodiment 33 (5mL 7.1g) turns back in the reactor, and cleans with nitrogen under 300 ℃. then, be that anhydrous hydrogen chloride and the fluoroform (HFC-23) of 20:1 is fed in the reactor jointly with mol ratio; Be that the GC-MS of 5 seconds .325 ℃ of following reactor effluents is analyzed as follows time of contact.

Component GC area %

HFC-23 71.9

HCFC-22 6.3

HCFC-21 2.6

HCC-201 8.2

CFC-13 0.7

CFC-12 0.2

Embodiment 50

1,1,1,3,3,3-HFC-236fa chlorination defluorinateization

With mol ratio is the anhydrous hydrogen chloride and 1,1,1,3,3 of 10:1, and 3-HFC-236fa (HFC-236fa) is fed in the reactor that contains the catalyst that uses among the embodiment 49 jointly; Be 10 seconds time of contact.The GC-MS of 325 ℃ of following reactor effluents is analyzed as follows.

Component GC area %

HFC-236fa 49.8

HFC-1225zc 0.9

HCFC-1224(two) 4.0

HCFC-235fa 0.7

HCFC-1223za 40.0

CFC-1213xa 3.7

Other product comprises HFC-143a, CFC-114/114a, CFC-1214, HCC-1120, HCFC-1222, HCC-1110.

Other Preparation of Catalyst- Preparation embodiment 51

Prepare 98% chromium/2% Co catalysts (550 ℃)

With [Cr (NH ₃) ₆] Cl ₃] (16.7684g, 64.4 mMs) and [Co (NH ₃) ₆] Cl ₃] (0.3513g, 1.31 mMs) be dissolved in the deionized water. then, in this solution, add aqueous ammonium hydroxide fully until precipitation.The sediment that filtration obtains, and in air, 110 ℃ dry 12 hours down. in agate mortar, fully grind the product that obtains, then in air, 550 ℃ of heating 12 hours down.

Show to have α-Cr by the XRD analysis sample ₂O ₃The principal crystalline phase of structure; TEM and EDS show and contain a spot of spinelle that contains cobalt and chromium mutually. contain the α-Cr of cobalt ₂O ₃Form with the 200-400nm crystal exists.XAS shows that cobalt is introduced α-Cr fully ₂O ₃In the lattice.

Claims

1. a crystallization cobalt replaces alpha-oxidation chromium, and wherein the chromium atom of 0.05-6 atom % is replaced by the trivalent cobalt atom in the alpha-oxidation chromium lattice.

2. carbon monoxide-olefin polymeric that contains chromium, it contains right and requires crystallization cobalt of 1 to replace alpha-oxidation chromium as containing the chromium component.

3. carbon monoxide-olefin polymeric that contains chromium, it contains by what the crystallization cobalt of handling claim 1 with fluorization agent replaced that alpha-oxidation chromium prepares and contains the chromium component.

4. one kind changes the method that fluorine distributes in hydrocarbon or halogenated hydrocarbons under the situation that catalyst exists, and it is characterized in that:

Use contains at least a composition that contains the chromium component as catalyst, describedly contains that crystallization cobalt that the chromium component is selected from claim 1 replaces alpha-oxidation chromium and the crystallization cobalt replacement alpha-oxidation chromium of the claim 1 handled with fluorization agent.

5. the method for claim 4, wherein under the situation that the described composition that uses as catalyst exists, by make the fluorine content that halogenated hydrocarbon compound or unsaturated hydrocarbon compound and hydrogen fluoride react to be increased in described halogenated hydrocarbon compound or the unsaturated hydrocarbon compound in gas phase.

6. the method for claim 4 is wherein under the situation that the described composition that uses as catalyst exists, by making halogenated hydrocarbon compound or hydrocarbon compound and HF and Cl ₂Reaction increases the fluorine content in described halogenated hydrocarbon compound or the hydrocarbon compound in gas phase.

7. the method for claim 4 wherein under the situation that the described composition that uses as catalyst exists, changes the distribution of fluorine in described halogenated hydrocarbon compound by the isomerization halogenated hydrocarbon compound.

8. the method for claim 4 wherein under the situation that the described composition that uses as catalyst exists, changes the distribution of fluorine in described halogenated hydrocarbon compound by disproportionation halogenated hydrocarbon compound in gas phase.

9. the method for claim 4 wherein under the situation that the described composition that uses as catalyst exists, reduces fluorine content in the described halogenated hydrocarbon compound by making the halogenated hydrocarbon compound dehydrofluorination.

10. the method for claim 4 wherein under the situation that the described composition that uses as catalyst exists, is reacted the fluorine content that reduces in the described halogenated hydrocarbon compound by making halogenated hydrocarbon compound and hydrogen chloride in gas phase.

11. one kind prepares the method for compositions that the crystallization cobalt that contains right requirement 1 replaces alpha-oxidation chromium, it comprises:

(a) make the solid co-precipitation by add ammonium hydroxide in the solution of solvable cobalt salt and solvable chromic salt, whenever have 1 mole of chromium just to contain at least 3 molar nitric acid roots in solution, the concentration of cobalt is the 0.05-6 mole % of chromium and cobalt total concentration in the solution; After joining the chromium at least 3 molar ammoniums/molar solution in the solution;

(b) be collected in the solid of the co-precipitation that forms in (a);

(c) the dry solid of collecting; With

(d) in the presence of oxygen, at the solid of 375-1000 ℃ of following calcination drying.

12. the method for claim 11, wherein step (d) is the solid of calcination drying in air.

13. the method for claim 11 or 12, wherein this soluble cobalt salt is a divalent cobalt.

14. the method for claim 13, wherein this soluble cobalt salt and chromic salts are nitrate.

15. the method for claim 14, wherein this soluble cobalt salt and chromic salts are nitric hydrate salt.

16. the method for claim 13 wherein exists in this aqueous solution and surpasses 3 molar nitric acids ammonium/mole chromium.